Counter electrode material for electrochromic devices

ABSTRACT

Various embodiments herein relate to electrochromic devices, methods of fabricating electrochromic devices, and apparatus for fabricating electrochromic devices. In a number of cases, the electrochromic device may be fabricated to include a particular counter electrode material. The counter electrode material may include a base anodically coloring material. The counter electrode material may further include one or more halogens. The counter electrode material may also include one or more additives.

INCORPORATION BY REFERENCE

An Application Data Sheet is filed concurrently with this specificationas part of the present application. Each application that the presentapplication claims benefit of or priority to as identified in theconcurrently filed Application Data Sheet is incorporated by referenceherein in their entireties and for all purposes.

BACKGROUND

Electrochromism is a phenomenon in which a material exhibits areversible electrochemically-mediated change in an optical property whenplaced in a different electronic state, typically by being subjected toa voltage change. The optical property is typically one or more ofcolor, transmittance, absorbance, and reflectance. One well knownelectrochromic material, for example, is tungsten oxide (WO₃). Tungstenoxide is a cathodic electrochromic material in which a colorationtransition, transparent to blue, occurs by electrochemical reduction.

Electrochromic materials may be incorporated into, for example, windowsand mirrors. The color, transmittance, absorbance, and/or reflectance ofsuch windows and mirrors may be changed by inducing a change in theelectrochromic material. One well known application of electrochromicmaterials, for example, is the rear view mirror in some cars. In theseelectrochromic rear view mirrors, the reflectivity of the mirror changesat night so that the headlights of other vehicles are not distracting tothe driver.

While electrochromism was discovered in the 1960's, electrochromicdevices still unfortunately suffer various problems and have not begunto realize their full commercial potential.

SUMMARY

The embodiments herein relate to electrochromic materials,electrochromic stacks, electrochromic devices, as well as methods andapparatus for making such materials, stacks, and devices. In variousembodiments, a counter electrode material includes a novel compositionof materials.

In one aspect of the disclosed embodiments, a method of fabricating anelectrochromic stack is provided, the method including: forming acathodically coloring layer including a cathodically coloringelectrochromic material; and forming an anodically coloring layerincluding an anodically coloring electrochromic material and one or morehalogens, the anodically coloring layer optionally including one or moreadditives, where the anodically coloring material includes at least onemetal selected from the group consisting of chromium (Cr), manganese(Mn), iron (Fe), cobalt (Co), nickel (Ni), rhodium (Rh), ruthenium (Ru),vanadium (V), and iridium (Ir), and where the optional additive includesa material selected from the group consisting of silver (Ag), arsenic(As), gold (Au), boron (B), cadmium (Cd), cesium (Cs), copper (Cu),europium (Eu), gallium (Ga), gadolinium (Gd), germanium (Ge), mercury(Hg), osmium (Os), lead (Pb), palladium (Pd), promethium (Pm), polonium(Po), platinum (Pt), radium (Ra), rubidium (Rb), terbium (Tb),technetium (Tc), thorium (Th), thallium (Tl), tungsten (W), andcombinations thereof.

In some embodiments, the metal in the anodically coloring electrochromicmaterial is selected from the group consisting of Cr, Mn, Fe, Co, Ni,Rh, Ir, and combinations thereof. In some such embodiments, the metal inthe anodically coloring electrochromic material is selected from thegroup consisting of Cr, Mn, Ni, Rh, Ir, and combinations thereof. Forinstance, the metal in the anodically coloring electrochromic materialmay be selected from the group consisting of Ni, Ir, and combinationsthereof. In a particular example, the metal in the anodically coloringelectrochromic material is Ni. In various embodiments, the anodicallycoloring layer includes the one or more additives, where the additiveincludes a material selected from the group consisting of Ga, Gd, Ge,Cu, and combinations thereof. The additive may include a materialselected from the group consisting of Ga, Gd, Ge, and combinationsthereof. In one example the additive includes Ge. In these or otherexamples, the additive includes Ga. In these or other examples, theadditive includes Gd. In these or other examples, the additive includesCu.

In some embodiments, the anodically coloring layer includes the one ormore additives, and the metal in the anodically coloring electrochromicmaterial is present in the anodically coloring layer at an atomic ratioequal to or greater than an atomic ratio of the metal in the additive.In some embodiments, the anodically coloring layer includes the one ormore additives, and the metal in the anodically coloring electrochromicmaterial is present in the anodically coloring layer at an atomic ratioequal to or greater than an atomic ratio of the additive in theanodically coloring electrochromic layer. In certain implementations,the anodically coloring layer includes nickel tungsten oxide and the oneor more halogens.

In another aspect of the disclosed embodiments, an electrochromic stackis provided, the electrochromic stack including: a cathodically coloringlayer including a cathodically coloring material; and an anodicallycoloring layer including an anodically coloring electrochromic materialand one or more halogens, the anodically coloring layer optionallyincluding one or more additives, where the anodically coloring materialincludes at least one metal selected from the group consisting ofchromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni),rhodium (Rh), ruthenium (Ru), vanadium (V), and iridium (Ir), and wherethe optional additive includes a material selected from the groupconsisting of silver (Ag), arsenic (As), gold (Au), boron (B), cadmium(Cd), cesium (Cs), copper (Cu), europium (Eu), gallium (Ga), gadolinium(Gd), germanium (Ge), mercury (Hg), osmium (Os), lead (Pb), palladium(Pd), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra),rubidium (Rb), terbium (Tb), technetium (Tc), thorium (Th), thallium(Tl), tungsten (W), and combinations thereof.

In some implementations, the metal in the anodically coloringelectrochromic material is selected from the group consisting of Cr, Mn,Fe, Co, Ni, Rh, Ir, and combinations thereof. In some such embodiments,the metal in the anodically coloring electrochromic material is selectedfrom the group consisting of Cr, Mn, Ni, Rh, Ir, and combinationsthereof. For instance, in some cases the metal in the anodicallycoloring electrochromic material is selected from the group consistingof Ni, Ir, and combinations thereof. In a particular example, the metalin the anodically coloring electrochromic material is Ni. In variousembodiments, the anodically coloring layer includes the one or moreadditives, and the additive includes a material selected from the groupconsisting of Ga, Gd, Ge, Cu, and combinations thereof. In some suchcases, the additive includes a material selected from the groupconsisting of Ga, Gd, Ge, and combinations thereof. In a particularexample, the additive includes Ge. In these or other examples, theadditive includes Ga. In these or other examples, the additive includesGd. In these or other examples, the additive includes Cu.

In certain implementations, the anodically coloring layer includes theone or more additives, and where the metal in the anodically coloringelectrochromic material is present in the anodically coloring layer atan atomic ratio equal to or greater than an atomic ratio of the metal inthe additive. In some embodiments, the anodically coloring layerincludes the one or more additives, and the metal in the anodicallycoloring electrochromic material is present in the anodically coloringlayer at an atomic ratio equal to or greater than an atomic ratio of theadditive in the anodically coloring electrochromic layer. In some cases,the anodically coloring layer includes nickel tungsten oxide and the oneor more halogens.

The anodically coloring layer is substantially amorphous in some cases.In certain embodiments, the anodically coloring layer includes anamorphous matrix of a first material having domains of a second materialscattered throughout the amorphous matrix.

In another aspect of the disclosed embodiments, an integrated depositionsystem for fabricating an electrochromic stack is provided, the systemincluding: a plurality of deposition stations aligned in series andinterconnected and operable to pass a substrate from one station to thenext without exposing the substrate to an external environment, wherethe plurality of deposition stations include: (i) a first depositionstation containing one or more material sources for depositing acathodically coloring layer; (ii) a second deposition station containingone or more material sources for depositing an anodically coloringlayer, where the one or more material sources for depositing theanodically coloring layer include at least a first metal and a halogen,the one or more material sources for depositing the anodically coloringlayer optionally including one or more additives, where the first metalis selected from the group consisting of chromium (Cr), manganese (Mn),iron (Fe), cobalt (Co), nickel (Ni), rhodium (Rh), and iridium (Ir),ruthenium (Ru), vanadium (V), and combinations thereof, and where theoptional additive is selected from the group consisting of silver (Ag),arsenic (As), gold (Au), boron (B), cadmium (Cd), cesium (Cs), copper(Cu), europium (Eu), gallium (Ga), gadolinium (Gd), germanium (Ge),mercury (Hg), osmium (Os), lead (Pb), palladium (Pd), promethium (Pm),polonium (Po), platinum (Pt), radium (Ra), rubidium (Rb), terbium (Tb),technetium (Tc), thorium (Th), thallium (Tl), tungsten (W), andcombinations thereof; and a controller containing program instructionsfor passing the substrate through the plurality of stations in a mannerthat deposits on the substrate (i) the cathodically coloring layer, and(ii) the anodically coloring layer to form a stack including at leastthe cathodically coloring layer and the anodically coloring layer.

In some embodiments, the one or more material sources for depositing theanodically coloring layer together include nickel, tungsten, and thehalogen. In some embodiments, at least one of the one or more materialsources for depositing the anodically coloring layer includes nickel,tungsten, and the halogen. In some implementations, the first metal isselected from the group consisting of Cr, Mn, Fe, Co, Ni, Rh, Ir, andcombinations thereof. In some such cases, the first metal is selectedfrom the group consisting of Cr, Mn, Ni, Rh, Ir, and combinationsthereof. In some embodiments, the first metal is selected from the groupconsisting of Ni, Ir, and combinations thereof. The first metal may beNi in some cases. In various embodiments, the one or more materialsources for depositing the anodically coloring layer include the one ormore additive, where the additive includes a material selected from thegroup consisting of Ga, Gd, Ge, Cu, and combinations thereof. In somesuch cases, the additive includes a material selected from the groupconsisting of Ga, Gd, Ge, and combinations thereof. In a particularexample, the additive includes Ge. In these or other examples, theadditive includes Ga. In these or other examples, the additive includesGd. In these or other examples, the additive includes Cu.

Other combinations of materials are possible as described furtherherein.

These and other features and advantages of the disclosed embodimentswill be described in further detail below, with reference to theassociated drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The following detailed description can be more fully understood whenconsidered in conjunction with the drawings in which:

FIG. 1 is a schematic cross-section of an electrochromic device inaccordance with embodiments.

FIG. 2 is a schematic cross-section of an electrochromic device in ableached state in accordance with specific embodiments.

FIG. 3 is a schematic cross-section of an electrochromic device in acolored state in accordance with specific embodiments.

FIG. 4 is a schematic cross-section of an electrochromic device with aparticle in the ion conducting layer causing a localized defect in thedevice.

FIG. 5A is a schematic cross-section of an electrochromic device with aparticle on the conductive layer prior to depositing the remainder ofthe electrochromic stack.

FIG. 5B is a schematic cross-section of the electrochromic device ofFIG. 5A, where a “pop off” defect is formed during electrochromic stackformation.

FIG. 5C is a schematic cross-section of the electrochromic device ofFIG. 5B, showing an electrical short that is formed from the pop offdefect once the second conductive is deposited.

FIG. 6A depicts a cross-sectional representation of an electrochromicwindow device in accord with the multistep process description providedin relation to FIG. 7A.

FIG. 6B depicts a top view of an electrochromic device showing locationof trenches cut into the device.

FIG. 7A depicts a process flow describing a method of fabricating anelectrochromic window.

FIGS. 7B-7D depict methods of fabricating an electrochromic stack whichis part of an electrochromic device according to certain embodiments.

FIG. 7E depicts a process flow for a conditioning process used tofabricate an electrochromic device according to certain embodiments.

FIG. 8A, depicts an integrated deposition system according to certainembodiments.

FIG. 8B depicts an integrated deposition system in a perspective view.

FIG. 8C depicts a modular integrated deposition system.

FIG. 8D depicts an integrated deposition system with two lithiumdeposition stations.

FIG. 8E depicts an integrated deposition system with one lithiumdeposition station.

DETAILED DESCRIPTION

Electrochromic Devices

A schematic cross-section of an electrochromic device 100 in accordancewith some embodiments is shown in FIG. 1. The electrochromic deviceincludes a substrate 102, a conductive layer (CL) 104, an electrochromiclayer (EC) 106 (sometimes also referred to as a cathodically coloringlayer), an ion conducting layer (IC) 108, a counter electrode layer (CE)110 (sometimes also referred to as an anodically coloring layer), and aconductive layer (CL) 114. Elements 104, 106, 108, 110, and 114 arecollectively referred to as an electrochromic stack 120. A voltagesource 116 operable to apply an electric potential across theelectrochromic stack 120 effects the transition of the electrochromicdevice from, e.g., a bleached state to a colored state. In otherembodiments, the order of layers is reversed with respect to thesubstrate. That is, the layers are in the following order: substrate,conductive layer, counter electrode layer, ion conducting layer,electrochromic material layer, conductive layer.

It should be understood that the reference to a transition between ableached state and colored state is non-limiting and suggests only oneexample, among many, of an electrochromic transition that may beimplemented. Unless otherwise specified herein, whenever reference ismade to a bleached-colored transition, the corresponding device orprocess encompasses other optical state transitions suchnon-reflective-reflective, transparent-opaque, etc. Further the term“bleached” refers to an optically neutral state, e.g., uncolored,transparent or translucent. Still further, unless specified otherwiseherein, the “color” of an electrochromic transition is not limited toany particular wavelength or range of wavelengths. As understood bythose of skill in the art, the choice of appropriate electrochromic andcounter electrode materials governs the relevant optical transition.

In certain embodiments, the electrochromic device reversibly cyclesbetween a bleached state and a colored state. In the bleached state, apotential is applied to the electrochromic stack 120 such that availableions in the stack that can cause the electrochromic material 106 to bein the colored state reside primarily in the counter electrode 110. Whenthe potential on the electrochromic stack is reversed, the ions aretransported across the ion conducting layer 108 to the electrochromicmaterial 106 and cause the material to enter the colored state. A moredetailed description of the transition from bleached to colored state,and from colored to bleached state, is included below in the descriptionof FIGS. 2 and 3, but first the individual layers of stack 120 will bedescribed in more detail in relation to FIG. 1.

In certain embodiments, all of the materials making up electrochromicstack 120 are inorganic, solid (i.e., in the solid state), or bothinorganic and solid. Because organic materials tend to degrade overtime, inorganic materials offer the advantage of a reliableelectrochromic stack that can function for extended periods of time.Materials in the solid state also offer the advantage of not havingcontainment and leakage issues, as materials in the liquid state oftendo. Each of the layers in the electrochromic device is discussed indetail, below. It should be understood that any one or more of thelayers in the stack may contain some amount of organic material, but inmany implementations one or more of the layers contains little or noorganic matter. The same can be said for liquids that may be present inone or more layers in small amounts. It should also be understood thatsolid state material may be deposited or otherwise formed by processesemploying liquid components such as certain processes employing sol-gelsor chemical vapor deposition.

Referring again to FIG. 1, voltage source 116 is typically a low voltageelectrical source and may be configured to operate in conjunction withradiant and other environmental sensors. Voltage source 116 may also beconfigured to interface with an energy management system, such as acomputer system that controls the electrochromic device according tofactors such as the time of year, time of day, and measuredenvironmental conditions. Such an energy management system, inconjunction with large area electrochromic devices (i.e., anelectrochromic window), can dramatically lower the energy consumption ofa building.

Any material having suitable optical, electrical, thermal, andmechanical properties may be used as substrate 102. Such substratesinclude, for example, glass, plastic, and mirror materials. Suitableplastic substrates include, for example acrylic, polystyrene,polycarbonate, allyl diglycol carbonate, SAN (styrene acrylonitrilecopolymer), poly(4-methyl-1-pentene), polyester, polyamide, etc. If aplastic substrate is used, it is preferably barrier protected andabrasion protected using a hard coat of, for example, a diamond-likeprotection coating, a silica/silicone anti-abrasion coating, or thelike, such as is well known in the plastic glazing art. Suitable glassesinclude either clear or tinted soda lime glass, including soda limefloat glass. The glass may be tempered or untempered. In someembodiments of electrochromic device 100 with glass, e.g. soda limeglass, used as substrate 102, there is a sodium diffusion barrier layer(not shown) between substrate 102 and conductive layer 104 to preventthe diffusion of sodium ions from the glass into conductive layer 104.

In some embodiments, the optical transmittance (i.e., the ratio oftransmitted radiation or spectrum to incident radiation or spectrum) ofsubstrate 102 is about 40 to 95%, e.g., about 90-92%. The substrate maybe of any thickness, as long as it has suitable mechanical properties tosupport the electrochromic stack 120. While the substrate 102 may be ofany size, in some embodiments, it is about 0.01 mm to 10 mm thick,preferably about 3 mm to 9 mm thick.

In some embodiments, the substrate is architectural glass. Architecturalglass is glass that is used as a building material. Architectural glassis typically used in commercial buildings, but may also be used inresidential buildings, and typically, though not necessarily, separatesan indoor environment from an outdoor environment. In certainembodiments, architectural glass is at least 20 inches by 20 inches, andcan be much larger, e.g., as large as about 72 inches by 120 inches.Architectural glass is typically at least about 2 mm thick.Architectural glass that is less than about 3.2 mm thick cannot betempered. In some embodiments with architectural glass as the substrate,the substrate may still be tempered even after the electrochromic stackhas been fabricated on the substrate. In some embodiments witharchitectural glass as the substrate, the substrate is a soda lime glassfrom a tin float line. The percent transmission over the visiblespectrum of an architectural glass substrate (i.e., the integratedtransmission across the visible spectrum) is generally greater than 80%for neutral substrates, but it could be lower for colored substrates.Preferably, the percent transmission of the substrate over the visiblespectrum is at least about 90% (e.g., about 90-92%). The visiblespectrum is the spectrum that a typical human eye will respond to,generally about 380 nm (purple) to about 780 nm (red). In some cases,the glass has a surface roughness of between about 10 and 30 nm.

On top of substrate 102 is conductive layer 104. In certain embodiments,one or both of the conductive layers 104 and 114 is inorganic and/orsolid. Conductive layers 104 and 114 may be made from a number ofdifferent materials, including conductive oxides, thin metalliccoatings, conductive metal nitrides, and composite conductors.Typically, conductive layers 104 and 114 are transparent at least in therange of wavelengths where electrochromism is exhibited by theelectrochromic layer. Transparent conductive oxides include metal oxidesand metal oxides doped with one or more metals. Examples of such metaloxides and doped metal oxides include indium oxide, indium tin oxide,doped indium oxide, tin oxide, doped tin oxide, zinc oxide, aluminumzinc oxide, doped zinc oxide, ruthenium oxide, doped ruthenium oxide andthe like. Since oxides are often used for these layers, they aresometimes referred to as “transparent conductive oxide” (TCO) layers.Thin metallic coatings that are substantially transparent may also beused. Examples of metals used for such thin metallic coatings includetransition metals including gold, platinum, silver, aluminum, nickelalloy, and the like. Thin metallic coatings based on silver, well knownin the glazing industry, are also used. Examples of conductive nitridesinclude titanium nitrides, tantalum nitrides, titanium oxynitrides, andtantalum oxynitrides. The conductive layers 104 and 114 may also becomposite conductors. Such composite conductors may be fabricated byplacing highly conductive ceramic and metal wires or conductive layerpatterns on one of the faces of the substrate and then over-coating withtransparent conductive materials such as doped tin oxides or indium tinoxide. Ideally, such wires should be thin enough as to be invisible tothe naked eye (e.g., about 100 μm or thinner).

In some embodiments, commercially available substrates such as glasssubstrates contain a transparent conductive layer coating. Such productsmay be used for both substrate 102 and conductive layer 104. Examples ofsuch glasses include conductive layer coated glasses sold under thetrademark TEC Glass™ by Pilkington, of Toledo, Ohio and SUNGATE™ 300 andSUNGATE™ 500 by PPG Industries of Pittsburgh, Pa. TEC Glass™ is a glasscoated with a fluorinated tin oxide conductive layer.

In some embodiments, the same conductive layer is used for bothconductive layers (i.e., conductive layers 104 and 114). In someembodiments, different conductive materials are used for each conductivelayer 104 and 114. For example, in some embodiments, TEC Glass™ is usedfor substrate 102 (float glass) and conductive layer 104 (fluorinatedtin oxide) and indium tin oxide is used for conductive layer 114. Asnoted above, in some embodiments employing TEC Glass™ there is a sodiumdiffusion barrier between the glass substrate 102 and TEC conductivelayer 104.

In some implementations, the composition of a conductive layer, asprovided for fabrication, should be chosen or tailored based on thecomposition of an adjacent layer (e.g., electrochromic layer 106 orcounter electrode layer 110) in contact with the conductive layer. Formetal oxide conductive layers, for example, conductivity is a functionof the number of oxygen vacancies in the conductive layer material, andthe number of oxygen vacancies in the metal oxide is impacted by thecomposition of the adjacent layer. Selection criteria for a conductivelayer may also include the material's electrochemical stability andability to avoid oxidation or more commonly reduction by a mobile ionspecies.

The function of the conductive layers is to spread an electric potentialprovided by voltage source 116 over surfaces of the electrochromic stack120 to interior regions of the stack, with very little ohmic potentialdrop. The electric potential is transferred to the conductive layersthough electrical connections to the conductive layers. In someembodiments, bus bars, one in contact with conductive layer 104 and onein contact with conductive layer 114, provide the electric connectionbetween the voltage source 116 and the conductive layers 104 and 114.The conductive layers 104 and 114 may also be connected to the voltagesource 116 with other conventional means.

In some embodiments, the thickness of conductive layers 104 and 114 isbetween about 5 nm and about 10,000 nm. In some embodiments, thethickness of conductive layers 104 and 114 are between about 10 nm andabout 1,000 nm. In other embodiments, the thickness of conductive layers104 and 114 are between about 10 nm and about 500 nm. In someembodiments where TEC Glass™ is used for substrate 102 and conductivelayer 104, the conductive layer is about 400 nm thick. In someembodiments where indium tin oxide is used for conductive layer 114, theconductive layer is about 100 nm to 400 nm thick (280 nm in oneembodiment). More generally, thicker layers of the conductive materialmay be employed so long as they provide the necessary electricalproperties (e.g., conductivity) and optical properties (e.g.,transmittance). Generally, the conductive layers 104 and 114 are as thinas possible to increase transparency and to reduce cost. In someembodiment, conductive layers are substantially crystalline. In someembodiment, conductive layers are crystalline with a high fraction oflarge equiaxed grains

The thickness of the each conductive layer 104 and 114 is alsosubstantially uniform. Smooth layers (i.e., low roughness, Ra) of theconductive layer 104 are desirable so that other layers of theelectrochromic stack 120 are more compliant. In one embodiment, asubstantially uniform conductive layer varies by no more than about +10%in each of the aforementioned thickness ranges. In another embodiment, asubstantially uniform conductive layer varies by no more than about +5%in each of the aforementioned thickness ranges. In another embodiment, asubstantially uniform conductive layer varies by no more than about +2%in each of the aforementioned thickness ranges.

The sheet resistance (R_(s)) of the conductive layers is also importantbecause of the relatively large area spanned by the layers. In someembodiments, the sheet resistance of conductive layers 104 and 114 isabout 5 to 30 Ohms per square. In some embodiments, the sheet resistanceof conductive layers 104 and 114 is about 15 Ohms per square. Ingeneral, it is desirable that the sheet resistance of each of the twoconductive layers be about the same. In one embodiment, the two layerseach have a sheet resistance of about 10-15 Ohms per square.

[1] Overlaying conductive layer 104 is cathodically coloring layer 106(also referred to as electrochromic layer 106). In some embodiments,electrochromic layer 106 is inorganic and/or solid, in typicalembodiments inorganic and solid. The electrochromic layer may containany one or more of a number of different cathodically coloringelectrochromic materials, including metal oxides. Such metal oxidesinclude, e.g., tungsten oxide (WO₃), molybdenum oxide (MoO₃), niobiumoxide (Nb₂O₅), titanium oxide (TiO₂), vanadium oxide (V₂O₅) and tantalumoxide (Ta₂O₅). In some embodiments, the cathodically coloring metaloxide is doped with one or more dopants such as lithium, sodium,potassium, molybdenum, vanadium, titanium, and/or other suitable metalsor compounds containing metals. Such dopants can be cathodicallycoloring, anodically coloring, or non-electrochromic, so long as thebulk material is cathodically coloring. For example, mixed oxides (e.g.,W-Mo oxide, W-V oxide) are also used in certain embodiments. Anelectrochromic layer 106 comprising a metal oxide is capable ofreceiving ions transferred from counter electrode layer 110.

In some embodiments, tungsten oxide or doped tungsten oxide is used forelectrochromic layer 106. In one embodiment, the electrochromic layer ismade substantially of WO_(x), where “x” refers to an atomic ratio ofoxygen to tungsten in the electrochromic layer, and x is between about2.7 and 3.5. It has been suggested that only sub-stoichiometric tungstenoxide exhibits electrochromism; i.e., stoichiometric tungsten oxide,WO₃, does not exhibit electrochromism. In a more specific embodiment,WO_(x), where x is less than 3.0 and at least about 2.7 is used for theelectrochromic layer. In another embodiment, the electrochromic layer isWO_(x), where x is between about 2.7 and about 2.9. Techniques such asRutherford Backscattering Spectroscopy (RBS) can identify the totalnumber of oxygen atoms which include those bonded to tungsten and thosenot bonded to tungsten. In some instances, tungsten oxide layers where xis 3 or greater exhibit electrochromism, presumably due to unboundexcess oxygen along with sub-stoichiometric tungsten oxide. In anotherembodiment, the tungsten oxide layer has stoichiometric or greateroxygen, where x is 3.0 to about 3.5.

In certain embodiments, the tungsten oxide is crystalline,nanocrystalline, or amorphous. In some embodiments, the tungsten oxideis substantially nanocrystalline, with grain sizes, on average, fromabout 5 nm to 50 nm (or from about 5 nm to 20 nm), as characterized bytransmission electron microscopy (TEM). The tungsten oxide morphologymay also be characterized as nanocrystalline using x-ray diffraction(XRD); XRD. For example, nanocrystalline electrochromic tungsten oxidemay be characterized by the following XRD features: a crystal size ofabout 10 to 100 nm (e.g., about 55 nm. Further, nanocrystalline tungstenoxide may exhibit limited long range order, e.g., on the order ofseveral (about 5 to 20) tungsten oxide unit cells.

The thickness of the electrochromic layer 106 depends on theelectrochromic material selected for the electrochromic layer. In someembodiments, the electrochromic layer 106 is about 50 nm to 2,000 nm, orabout 200 nm to 700 nm. In some embodiments, the electrochromic layer isabout 300 nm to about 500 nm. The thickness of the electrochromic layer106 is also substantially uniform. In one embodiment, a substantiallyuniform electrochromic layer varies only about ±10% in each of theaforementioned thickness ranges. In another embodiment, a substantiallyuniform electrochromic layer varies only about ±5% in each of theaforementioned thickness ranges. In another embodiment, a substantiallyuniform electrochromic layer varies only about ±3% in each of theaforementioned thickness ranges.

Generally, in electrochromic materials, the colorization (or change inany optical property—e.g., absorbance, reflectance, and transmittance)of the electrochromic material is caused by reversible ion insertioninto the material (e.g., intercalation) and a corresponding injection ofa charge balancing electron. Typically some fraction of the ionresponsible for the optical transition is irreversibly bound up in theelectrochromic material. As explained below some or all of theirreversibly bound ions are used to compensate “blind charge” in thematerial. In most electrochromic materials, suitable ions includelithium ions (Li⁺) and hydrogen ions (H⁺) (i.e., protons). In somecases, however, other ions will be suitable. These include, for example,deuterium ions (D⁺), sodium ions (Na⁺), potassium ions (K⁺), calciumions (Ca⁺⁺), barium ions (Ba⁺⁺), strontium ions (Sr⁺⁺), and magnesiumions (Mg⁺⁺). In various embodiments described herein, lithium ions areused to produce the electrochromic phenomena. Intercalation of lithiumions into tungsten oxide (WO_(3-y) (0<y≤˜0.3)) causes the tungsten oxideto change from transparent (bleached state) to blue (colored state).

Referring again to FIG. 1, in electrochromic stack 120, ion conductinglayer 108 overlays electrochromic layer 106. On top of ion conductinglayer 108 is counter electrode layer 110. In some embodiments, counterelectrode layer 110 is inorganic and/or solid. The counter electrodelayer may comprise one or more of a number of different materials thatare capable of serving as reservoirs of ions when the electrochromicdevice is in the bleached state. During an electrochromic transitioninitiated by, e.g., application of an appropriate electric potential,the counter electrode layer transfers some or all of the ions it holdsto the electrochromic layer, changing the electrochromic layer to thecolored state. Concurrently, the counter electrode layer colors with theloss of ions.

In some embodiments, suitable materials for the counter electrode layerinclude a base anodically coloring electrochromic material and one ormore additive materials. The base anodically coloring material may be,for example, cobalt oxide, chromium oxide, iron oxide, iridium oxide,manganese oxide, nickel oxide, rhodium oxide, ruthenium oxide, vanadiumoxide, and any combination thereof. In certain embodiments, the baseanodically coloring electrochromic material includes a material selectedfrom the group consisting of chromium oxide, manganese oxide, ironoxide, cobalt oxide, nickel oxide, rhodium oxide, and iridium oxide. Inone example, the base anodically coloring electrochromic material isselected from the group consisting of chromium oxide, manganese oxide,nickel oxide, rhodium oxide, and iridium oxide. In another example, thebase anodically coloring electrochromic material includes nickel oxideand/or iridium oxide.

The additive in various cases may be selected from the group consistingof silver (Ag), arsenic (As), gold (Au), boron (B), cadmium (Cd), cesium(Cs), copper (Cu), europium (Eu), gallium (Ga), gadolinium (Gd),germanium (Ge), mercury (Hg), osmium (Os), lead (Pb), palladium (Pd),promethium (Pm), polonium (Po), platinum (Pt), radium (Ra), rubidium(Rb), terbium (Tb), technetium (Tc), thorium (Th), thallium (Tl), andcombinations thereof. In some embodiments, the additive is selected fromthe group consisting of Ga, Gd, Ge, Cu, and combinations thereof. Theadditive may include at least one of Ga, Gd, and Ge. In someimplementations, the additive may include at least one of Ge and Cu. Onereason that germanium may be especially useful is thatgermanium/germanium oxide show a high optical band gap.

In certain embodiments, the concentration of the additive metal materialmay be less than about 50% atomic, less than about 25% atomic, less thanabout 10% atomic, less than about 5% atomic, less than about 2% atomic,or less than about 1% atomic. The additional material should be added atan amount/concentration sufficient to maintain the anodic coloringproperties of the electrode. The proper balance between the baseanodically coloring electrochromic material and the additive depends onthe particular materials being used, though one of ordinary skill in theart is readily capable of determining appropriate concentrations tomaintain the overall anodically coloring property of the counterelectrode.

In certain embodiments, a halogen (i.e., one or more of fluorine (F),chlorine (Cl), bromine (Br), iodine (I), and astatine (As)) may be addedto the counter electrode, for example to promote improved colorqualities. The halogen(s) may be provided at a particular concentrationin certain embodiments, for example at any of the concentrationsdescribed above with respect to the additives. In some cases, theadditive concentrations listed above may correspond to the concentrationof additive(s)+halogen(s).

In a particular example, the counter electrode material may includenickel, tungsten, oxygen, and one or more halogen. Particular examplesinclude NiWO combined with fluorine, NiWO combined with chlorine, NiWOcombined with bromine, NiWO combined with iodine, and NiWO combined withastatine. As mentioned, combinations of different halogens may also beused in some cases. The halogen may be doped or otherwise combined withthe other elements in the counter electrode material.

Halogens may also be combined with other counter electrode materials,for example to improve color qualities of the counter electrode. Invarious embodiments, a counter electrode material may include a baseanodically coloring material and one or more halogen. The baseanodically coloring material may be any of the base anodically coloringmaterials listed herein.

The counter electrode layer may include nickel oxide in combination withan additive in certain cases. Example materials for the counterelectrode layer in this case may include nickel silver oxide, nickelarsenic oxide, nickel gold oxide, nickel boron oxide, nickel cadmiumoxide, nickel cesium oxide, nickel copper oxide, nickel europium oxide,nickel gadolinium oxide, nickel gallium oxide, nickel germanium oxide,nickel mercury oxide, nickel osmium oxide, nickel lead oxide, nickelpalladium oxide, nickel promethium oxide, nickel polonium oxide, nickelplatinum oxide, nickel radium oxide, nickel rubidium oxide, nickelterbium oxide, nickel technetium oxide, nickel thorium oxide, nickelthallium oxide, and combinations thereof.

In these or other cases, the counter electrode layer may include cobaltoxide in combination with an additive. Example materials for the counterelectrode layer in this case may include cobalt silver oxide, cobaltarsenic oxide, cobalt gold oxide, cobalt boron oxide, cobalt cadmiumoxide, cobalt cesium oxide, cobalt copper oxide, cobalt europium oxide,cobalt gadolinium oxide, cobalt gallium oxide, cobalt germanium oxide,cobalt mercury oxide, cobalt osmium oxide, cobalt lead oxide, cobaltpalladium oxide, cobalt promethium oxide, cobalt polonium oxide, cobaltplatinum oxide, cobalt radium oxide, cobalt rubidium oxide, cobaltterbium oxide, cobalt technetium oxide, cobalt thorium oxide, cobaltthallium oxide, and combinations thereof.

Where the counter electrode layer includes chromium oxide, examplematerials for the counter electrode layer may include chromium silveroxide, chromium arsenic oxide, chromium gold oxide, chromium boronoxide, chromium cadmium oxide, chromium cesium oxide, chromium copperoxide, chromium europium oxide, chromium gadolinium oxide, chromiumgallium oxide, chromium germanium oxide, chromium mercury oxide,chromium osmium oxide, chromium lead oxide, chromium palladium oxide,chromium promethium oxide, chromium polonium oxide, chromium platinumoxide, chromium radium oxide, chromium rubidium oxide, chromium terbiumoxide, chromium technetium oxide, chromium thorium oxide, chromiumthallium oxide, and combinations thereof.

Where the counter electrode layer includes iron oxide in combinationwith an additive, example materials for the counter electrode layer mayinclude iron silver oxide, iron arsenic oxide, iron gold oxide, ironboron oxide, iron cadmium oxide, iron cesium oxide, iron copper oxide,iron europium oxide, iron gadolinium oxide, iron gallium oxide, irongermanium oxide, iron mercury oxide, iron osmium oxide, iron lead oxide,iron palladium oxide, iron promethium oxide, iron polonium oxide, ironplatinum oxide, iron radium oxide, iron rubidium oxide, iron terbiumoxide, iron technetium oxide, iron thorium oxide, iron thallium oxide,and combinations thereof.

Where the counter electrode layer includes iridium oxide in combinationwith an additive, example materials for the counter electrode layer mayinclude iridium silver oxide, iridium arsenic oxide, iridium gold oxide,iridium boron oxide, iridium cadmium oxide, iridium cesium oxide,iridium copper oxide, iridium europium oxide, iridium gadolinium oxide,iridium gallium oxide, iridium germanium oxide, iridium mercury oxide,iridium osmium oxide, iridium lead oxide, iridium palladium oxide,iridium promethium oxide, iridium polonium oxide, iridium platinumoxide, iridium radium oxide, iridium rubidium oxide, iridium terbiumoxide, iridium technetium oxide, iridium thorium oxide, iridium thalliumoxide, and combinations thereof.

Where the counter electrode layer includes manganese oxide incombination with an additive, example materials for the counterelectrode layer may include manganese silver oxide, manganese arsenicoxide, manganese gold oxide, manganese boron oxide, manganese cadmiumoxide, manganese cesium oxide, manganese copper oxide, manganeseeuropium oxide, manganese gadolinium oxide, manganese gallium oxide,manganese germanium oxide, manganese mercury oxide, manganese osmiumoxide, manganese lead oxide, manganese palladium oxide, manganesepromethium oxide, manganese polonium oxide, manganese platinum oxide,manganese radium oxide, manganese rubidium oxide, manganese terbiumoxide, manganese technetium oxide, manganese thorium oxide, manganesethallium oxide, and combinations thereof.

Where the counter electrode layer includes rhodium oxide in combinationwith an additive, example materials for the counter electrode layer mayinclude rhodium silver oxide, rhodium arsenic oxide, rhodium gold oxide,rhodium boron oxide, rhodium cadmium oxide, rhodium cesium oxide,rhodium copper oxide, rhodium europium oxide, rhodium gadolinium oxide,rhodium gallium oxide, rhodium germanium oxide, rhodium mercury oxide,rhodium osmium oxide, rhodium lead oxide, rhodium palladium oxide,rhodium promethium oxide, rhodium polonium oxide, rhodium platinumoxide, rhodium radium oxide, rhodium rubidium oxide, rhodium terbiumoxide, rhodium technetium oxide, rhodium thorium oxide, rhodium thalliumoxide, and combinations thereof.

Where the counter electrode layer includes ruthenium oxide incombination with an additive, example materials for the counterelectrode layer may include ruthenium silver oxide, ruthenium arsenicoxide, ruthenium gold oxide, ruthenium boron oxide, ruthenium cadmiumoxide, ruthenium cesium oxide, ruthenium copper oxide, rutheniumeuropium oxide, ruthenium gadolinium oxide, ruthenium gallium oxide,ruthenium germanium oxide, ruthenium mercury oxide, ruthenium osmiumoxide, ruthenium lead oxide, ruthenium palladium oxide, rutheniumpromethium oxide, ruthenium polonium oxide, ruthenium platinum oxide,ruthenium radium oxide, ruthenium rubidium oxide, ruthenium terbiumoxide, ruthenium technetium oxide, ruthenium thorium oxide, rutheniumthallium oxide, and combinations thereof.

Where the counter electrode layer includes vanadium oxide in combinationwith an additive, example materials for the counter electrode layer mayinclude vanadium silver oxide, vanadium arsenic oxide, vanadium goldoxide, vanadium boron oxide, vanadium cadmium oxide, vanadium cesiumoxide, vanadium copper oxide, vanadium europium oxide, vanadiumgadolinium oxide, vanadium gallium oxide, vanadium germanium oxide,vanadium mercury oxide, vanadium osmium oxide, vanadium lead oxide,vanadium palladium oxide, vanadium promethium oxide, vanadium poloniumoxide, vanadium platinum oxide, vanadium radium oxide, vanadium rubidiumoxide, vanadium terbium oxide, vanadium technetium oxide, vanadiumthorium oxide, vanadium thallium oxide, and combinations thereof.

The counter electrode layer may include one or more, in some cases twoor more, of the materials listed in the previous paragraphs. Forexample, nickel germanium oxide may be combined with iridium galliumoxide, etc.

Some particular example materials for the counter electrode include, butare not limited to, nickel oxide, nickel tungsten oxide, nickel vanadiumoxide, nickel chromium oxide, nickel aluminum oxide, nickel manganeseoxide, nickel magnesium oxide, chromium oxide, iron oxide, cobalt oxide,rhodium oxide, iridium oxide, manganese oxide, Prussian blue. Thematerials (e.g., metal and oxygen) may be provided at differentstoichiometric ratios as appropriate for a given application. Counterelectrodes of other materials may be used, and in some cases maycomprise cerium titanium oxide, cerium zirconium oxide, vanadium oxide,and mixtures of oxides (e.g., a mixture of Ni₂O₃ and WO₃), as notedabove. Doped formulations of these oxides may also be used, with dopantsincluding, e.g., tantalum and tungsten and the other additives listedabove. Because counter electrode layer 110 contains the ions used toproduce the electrochromic phenomenon in the electrochromic materialwhen the electrochromic material is in the bleached state, the counterelectrode preferably has high transmittance and a neutral color when itholds significant quantities of these ions. In some embodiments,nickel-tungsten oxide (NiWO) is used in the counter electrode layer,optionally along with an additional additive listed above, andoptionally with one or more halogen. In certain embodiments, the amountof nickel present in the nickel-tungsten oxide can be up to about 90% byweight of the nickel-tungsten oxide. In a specific embodiment, the massratio of nickel to tungsten in the nickel-tungsten oxide is betweenabout 4:6 and 6:4 (e.g., about 1:1). In one embodiment, the NiWO isbetween about 15% (atomic) Ni and about 60% Ni; between about 10% W andabout 40% W; between about 30% O and about 75% O; and optionallyincludes one or more additional additives and/or halogens as describedherein. In another embodiment, the NiWO is between about 30% (atomic) Niand about 45% Ni; between about 10% W and about 25% W; between about 35%O and about 50% O; and optionally includes one or more additives and/orhalogens as described herein.

When charge is removed from a counter electrode 110 (i.e., ions aretransported from the counter electrode 110 to the electrochromic layer106), the counter electrode layer will turn from a transparent state toa tinted state. For instance, a nickel tungsten oxide counter electrode110 will switch from a transparent state to a brown state. Other counterelectrode materials may exhibit different colors in their tinted statesand/or may be relatively more transparent in their clear states comparedto a nickel tungsten oxide counter electrode.

The counter electrode morphology may be crystalline, nanocrystalline, oramorphous. In some embodiments, where the counter electrode layer isnickel-tungsten oxide along with an additive listed above, the counterelectrode material is amorphous or substantially amorphous.Substantially amorphous nickel-tungsten oxide counter electrodes havebeen found to perform better, under some conditions, in comparison totheir crystalline counterparts. The amorphous state of thenickel-tungsten oxide may be obtained though the use of certainprocessing conditions, described below. While not wishing to be bound toany theory or mechanism, it is believed that amorphous nickel-tungstenoxide is produced by relatively higher energy atoms in the sputteringprocess. Higher energy atoms are obtained, for example, in a sputteringprocess with higher target powers, lower chamber pressures (i.e., highervacuum), and smaller source to substrate distances. Under the describedprocess conditions, higher density films, with better stability underUV/heat exposure are produced.

In some embodiments, the counter electrode morphology may includemicrocrystalline, nanocrystalline and/or amorphous phases. For example,the counter electrode may be, e.g., a material with an amorphous matrixhaving nanocrystals distributed throughout. In certain embodiments, thenanocrystals constitute about 50% or less of the counter electrodematerial, about 40% or less of the counter electrode material, about 30%or less of the counter electrode material, about 20% or less of thecounter electrode material or about 10% or less of the counter electrodematerial (by weight or by volume depending on the embodiment). Incertain embodiments, the nanocrystals have a maximum diameter of lessthan about 50 nm, in some cases less than about 25 nm, less than about10 nm, or less than about 5 nm. In some cases, the nanocrystals have amean diameter of about 50 nm or less, or about 10 nm or less, or about 5nm or less (e.g., about 1-10 nm). In certain embodiments, it isdesirable to have a nanocrystal size distribution where at least about50% of the nanocrystals have a diameter within 1 standard deviation ofthe mean nanocrystal diameter, for example where at least about 75% ofthe nanocrystals have a diameter within 1 standard deviation of the meannanocrystal diameter or where at least about 90% of the nanocrystalshave a diameter within 1 standard deviation of the mean nanocrystaldiameter. It has been found that counter electrodes with an amorphousmatrix tend to operate more efficiently compared to counter electrodesthat are relatively more crystalline. In certain embodiments, theadditive may form a host matrix in which domains of the base anodicallycoloring material may be found. In various cases, the host matrix issubstantially amorphous. In certain embodiments, the only crystallinestructures in the counter electrode are formed from the base anodicallycoloring electrochromic material, in, e.g., oxide form. As mentioned,the additives may contribute to forming an amorphous host matrix that isnot substantially crystalline, but which incorporates domains (e.g.,nanocrystals in some cases) of the base anodically coloringelectrochromic material. In other embodiments, the additive and theanodically coloring base material together form a chemical compound withcovalent and/or ionic bonding. The compound may be crystalline,amorphous, or any combination thereof. In other embodiments, theanodically coloring base material forms a host matrix in which domainsof the additive exist as discrete phases or pockets.

In some embodiments, the thickness of the counter electrode is about 50nm about 650 nm. In some embodiments, the thickness of the counterelectrode is about 100 nm to about 400 nm, preferably in the range ofabout 200 nm to 300 nm. The thickness of the counter electrode layer 110is also substantially uniform. In one embodiment, a substantiallyuniform counter electrode layer varies only about ±10% in each of theaforementioned thickness ranges. In another embodiment, a substantiallyuniform counter electrode layer varies only about ±5% in each of theaforementioned thickness ranges. In another embodiment, a substantiallyuniform counter electrode layer varies only about ±3% in each of theaforementioned thickness ranges.

The amount of ions held in the counter electrode layer during thebleached state (and correspondingly in the electrochromic layer duringthe colored state) and available to drive the electrochromic transitiondepends on the composition of the layers as well as the thickness of thelayers and the fabrication method. Both the electrochromic layer and thecounter electrode layer are capable of supporting available charge (inthe form of lithium ions and electrons) in the neighborhood of severaltens of millicoulombs per square centimeter of layer surface area. Thecharge capacity of an electrochromic film is the amount of charge thatcan be loaded and unloaded reversibly per unit area and unit thicknessof the film by applying an external voltage or potential. In oneembodiment, the WO₃ layer has a charge capacity of between about 30 andabout 150 mC/cm²/micron. In another embodiment, the WO₃ layer has acharge capacity of between about 50 and about 100 mC/cm²/micron. In oneembodiment, a NiWO layer including an optional additional additiveand/or halogen listed above has a charge capacity of between about 75and about 200 mC/cm²/micron. In another embodiment, the NiWO layer (withan optional additional additive and/or halogen listed above) has acharge capacity of between about 100 and about 150 mC/cm²/micron.

In between electrochromic layer 106 and counter electrode layer 110,there is an ion conducting layer 108. Ion conducting layer 108 serves asa medium through which ions are transported (in the manner of anelectrolyte) when the electrochromic device transforms between thebleached state and the colored state. Preferably, ion conducting layer108 is highly conductive to the relevant ions for the electrochromic andthe counter electrode layers, but has sufficiently low electronconductivity that negligible electron transfer takes place during normaloperation. A thin ion conducting layer with high ionic conductivitypermits fast ion conduction and hence fast switching for highperformance electrochromic devices. In certain embodiments, the ionconducting layer 108 is inorganic and/or solid. When fabricated from amaterial and in a manner that produces relatively few defects, the ionconductor layer can be made very thin to produce a high performancedevice. In various implementations, the ion conductor material has anionic conductivity of between about 10⁸ Siemens/cm or ohm⁻¹ cm⁻¹ andabout 10⁹ Siemens/cm or ohm⁻¹ cm⁻¹ and an electronic resistance of about10¹¹ ohms-cm.

Examples of suitable materials for the ion conductor layer includelithium silicate, lithium aluminum silicate, lithium oxide, lithiumtungstate, lithium aluminum borate, lithium borate, lithium zirconiumsilicate, lithium niobate, lithium borosilicate, lithiumphosphosilicate, lithium nitride, lithium oxynitride, lithium aluminumfluoride, lithium phosphorus oxynitride (LiPON), lithium lanthanumtitanate (LLT), lithium tantalum oxide, lithium zirconium oxide, lithiumsilicon carbon oxynitride (LiSiCON), lithium titanium phosphate, lithiumgermanium vanadium oxide, lithium zinc germanium oxide, and otherceramic materials that allow lithium ions to pass through them whilehaving a high electrical resistance (blocking electron movementtherethrough). Any material, however, may be used for the ion conductinglayer 108 provided it can be fabricated with low defectivity and itallows for the passage of ions between the counter electrode layer 110to the electrochromic layer 106 while substantially preventing thepassage of electrons.

In certain embodiments, the ion conducting layer is crystalline,nanocrystalline, or amorphous. Typically, the ion conducting layer isamorphous. In another embodiment, the ion conducting layer isnanocrystalline. In yet another embodiment, the ion conducting layer iscrystalline.

In some embodiments, a silicon-aluminum-oxide (SiAlO) is used for theion conducting layer 108. In a specific embodiment, a silicon/aluminumtarget used to fabricate the ion conductor layer via sputtering containsbetween about 6 and about 20 atomic percent aluminum. This defines theratio of silicon to aluminum in the ion conducting layer. In someembodiments, the silicon-aluminum-oxide ion conducting layer 108 isamorphous.

The thickness of the ion conducting layer 108 may vary depending on thematerial. In some embodiments, the ion conducting layer 108 is about 5nm to 100 nm thick, preferably about 10 nm to 60 nm thick. In someembodiments, the ion conducting layer is about 15 nm to 40 nm thick orabout 25 nm to 30 nm thick. The thickness of the ion conducting layer isalso substantially uniform. In one embodiment, a substantially uniformion conducting layer varies by not more than about ±10% in each of theaforementioned thickness ranges. In another embodiment, a substantiallyuniform ion conducting layer varies by not more than about ±5% in eachof the aforementioned thickness ranges. In another embodiment, asubstantially uniform ion conducting layer varies by not more than about±3% in each of the aforementioned thickness ranges.

Ions transported across the ion conducting layer between theelectrochromic layer and the counter electrode layer serve to effect acolor change in the electrochromic layer (i.e., change theelectrochromic device from the bleached state to the colored state).Depending on the choice of materials for the electrochromic devicestack, such ions include lithium ions (Li⁺) and hydrogen ions (H⁺)(i.e., protons). As mentioned above, other ions may be employed incertain embodiments. These include deuterium ions (D⁺), sodium ions(Na⁺), potassium ions (K⁺), calcium ions (Ca⁺⁺), barium ions (Ba⁺⁺),strontium ions (Sr⁺⁺), and magnesium ions (Mg⁺⁺).

As noted, the ion conducting layer 108 should have very few defects.Among other problems, defects in the ion conducting layer may result inshort circuits between the electrochromic layer and the counterelectrode layer (described in more detail below in relation to FIG. 4).A short circuit occurs when electrical communication is establishedbetween oppositely charged conductive layers, e.g. a conductive particlemakes contact with each of two conductive and electrically chargedlayers (as opposed to a “pin hole” which is a defect which does notcreate a short circuit between oppositely charged conductive layers).When a short circuit occurs, electrons rather than ions migrate betweenthe electrochromic layer and the counter electrode, typically resultingin bright spots (i.e., spots where the window does not switch butinstead, maintains the open circuit coloration which is often muchlighter than the colored state) at the location of the short when theelectrochromic device is otherwise in the colored state. The ionconducting layer is preferably as thin as possible, without any shortsbetween the electrochromic layer and the counter electrode layer. Asindicated, low defectivity in the ion conducting layer 108 (or elsewherein the electrochromic device) allows for a thinner ion conducting layer108. Ion transport between the electrochromic layer and the counterelectrode layer with electrochemical cycling is faster when using a thinion conducting layer. To generalize, the defectivity criteria specifiedherein may apply to any specific layer (ion conducting layer orotherwise) in the stack or to the stack as a whole or to any portionthereof. Defectivity criteria will be further discussed below.

The electrochromic device 100 may include one or more additional layers(not shown) such as one or more passive layers. Passive layers used toimprove certain optical properties may be included in electrochromicdevice 100. Passive layers for providing moisture or scratch resistancemay also be included in the electrochromic device 100. For example, theconductive layers may be treated with anti-reflective or protectiveoxide or nitride layers. Other passive layers may serve to hermeticallyseal the electrochromic device 100.

FIG. 2 is a schematic cross-section of an electrochromic device in ableached state (or transitioning to a bleached state). In accordancewith specific embodiments, the electrochromic device 200 includes atungsten oxide electrochromic layer (EC) 206 and a counter electrodelayer (CE) 210 as described herein. In some cases, the tungsten oxideelectrochromic layer 206 has a nanocrystalline, or substantiallynanocrystalline, morphology. In some embodiments, the counter electrodelayer 210 has an amorphous, or substantially amorphous, morphology. Insome embodiments, the weight percent ratio of tungsten to nickel in thecounter electrode is about 0.40-0.60

The electrochromic device 200 also includes substrate 202, conductivelayer (CL) 204, ion conducting layer (IC) 208, and conductive layer (CL)214. In some embodiments, the substrate 202 and conductive layer 204together comprise a TEC-Glass™. As indicated, the electrochromic devicesdescribed herein, such as those of FIG. 2, often find beneficialapplication in architectural glass. Thus, in some embodiments, thesubstrate 202 is of the dimensions such that it may be classified asarchitectural glass. In some embodiments, the conductive layer 214 isindium tin oxide (ITO). In some embodiments, the ion conducting layer208 is a silicon-aluminum-oxide.

The voltage source 216 is configured to apply a potential toelectrochromic stack 220 through suitable connections (e.g., bus bars)to conductive layers 204 and 214. In some embodiments, the voltagesource is configured to apply a potential of about 2 volts in order todrive a transition of the device from one optical state to another. Thepolarity of the potential as shown in FIG. 2 is such that the ions(lithium ions in this example) primarily reside in the counter electrodelayer 210.

In embodiments employing an electrochromic layer of tungsten oxide and acounter electrode layer (e.g., of nickel tungsten oxide with an additiveas described above, or another counter electrode material), the ratio ofthe electrochromic layer thickness to the counter electrode layerthickness may be about 1.7:1 to 2.3:1 (e.g., about 2:1). In someembodiments, the electrochromic tungsten oxide layer is about 200 nm to700 nm thick. In further embodiments, the electrochromic tungsten oxidelayer is about 400 nm to 500 nm thick. In some embodiments, the counterelectrode layer is about 100 nm to 350 nm thick. In further embodiments,the counter electrode layer is about 200 nm to 250 nm thick. In yetfurther embodiments, the counter electrode layer is about 240 nm thick.Also, in some embodiments, the silicon-aluminum-oxide ion conductinglayer 208 is about 10 nm to 100 nm thick. In further embodiments, thesilicon-aluminum-oxide ion conducting layer is about 20 nm to 50 nmthick.

As indicated above, electrochromic materials may contain blind charge.The blind charge in an electrochromic material is the charge (e.g.,negative charge in the case of tungsten oxide electrochromic material)that exists in the material as fabricated, absent compensation byoppositely charged ions or other charge carriers. With tungsten oxide,for example, the magnitude of the blind charge depends upon the excessoxygen concentration during sputtering of the tungsten oxide.Functionally, blind charge must be compensated before the ions employedto transform the electrochromic material can effectively change anoptical property of the electrochromic material. Without priorcompensation of the blind charge, ions supplied to an electrochromicmaterial will irreversibly incorporate in the material and have noeffect on the optical state of the material. Thus, an electrochromicdevice is typically provided with ions, such as lithium ions or protons,in an amount sufficient both to compensate the blind charge and toprovide a supply of ions for reversibly switching the electrochromicmaterial between two optical states. In many known electrochromicdevices, charge is lost during the first electrochemical cycle incompensating blind charge.

In some embodiments, lithium is present in the electrochromic stack 220in an amount sufficient to compensate the blind charge in theelectrochromic layer 206 and then an additional amount of about 1.5 to2.5 times the amount used to compensate the blind charge (by mass) inthe stack (initially in the counter electrode layer 210 for example).That is, there is about 1.5 to 2.5 times the amount of lithium needed tocompensate the blind charge that is provided for reversible cyclingbetween the electrochromic layer 206 and the counter electrode layer 210in the electrochromic stack 220. In some embodiments, there are enoughlithium in the electrochromic stack 220 to compensate the blind chargein the electrochromic layer 206 and then about two times this amount (bymass) in the counter electrode layer 210 or elsewhere in the stack.

FIG. 3 is a schematic cross-section of electrochromic device 200 shownin FIG. 2 but in a colored state (or transitioning to a colored state).In FIG. 3, the polarity of voltage source 216 is reversed, so that theelectrochromic layer is made more negative to accept additional lithiumions, and thereby transition to the colored state. As shown, lithiumions are transported across the ion conducting layer 208 to the tungstenoxide electrochromic layer 206. The tungsten oxide electrochromic layer206 is shown in the colored state. The counter electrode 210 is alsoshown in the colored state. As explained, the counter electrode materialbecomes progressively more opaque as it gives up (deintercalates)lithium ions. In this example, there is a synergistic effect where thetransition to colored states for both layers 206 and 210 are additivetoward reducing the amount of light transmitted through the stack andsubstrate.

In certain embodiments, electrochromic devices of the types describedabove are very reliable, often substantially more so than counterpartdevices of the prior art. Reliability may be characterized by variousmetrics. Some of these are described in ASTM E2141-06 (Standard TestMethods for Assessing the Durability of Absorptive ElectrochromicCoatings on Sealed Insulating Glass Units). In some specific cases, thedevices are able to cycle between two distinct optical states (e.g.,between bleached and colored) over 50,000 times while maintaining aratio of the bleached T_(vis) to colored T_(vis) (also know as PTR orphotopic transmission ratio) of >4. The longevity of theseelectrochromic devices makes them suitable for use in applications wherethe electrochromic devices are expected to be in place for tens ofyears. Furthermore, the electrochromic devices in certain embodimentsare able to cycle between bleached and unbleached states without losingtransmissivity in the bleached state and without degradation of thecolor or other property in the unbleached state. In some cases, the highreliability of an electrochromic device in accordance with embodimentsherein described is due in part to a design in which the thickness ofthe electrochromic layer and/or the thickness of the counter electrodelayer in a stack do not substantially change during electrochemicalcycling of the electrochromic device from their as deposited, postlithiation thickness (e.g., by no more than about 4%).

As indicated above, many electrochromic devices as described herein havea reduced number of defects; i.e., considerably fewer than are presentin comparable prior devices. As used herein, the term “defect” refers toa defective point or region of an electrochromic device. Defects may becaused by electrical shorts or by pinholes. Further, defects may becharacterized as visible or non-visible. In general, a defect in anelectrochromic device does not change optical state (e.g., color) inresponse to an applied potential that is sufficient to causenon-defective regions of the electrochromic device to color or otherwisechange optical state. Often a defect will be manifest as visuallydiscernable anomalies in the electrochromic window or other device. Suchdefects are referred to herein as “visible” defects. Other defects areso small that they are not visually noticeable to the observer in normaluse (e.g., such defects do not produce a noticeable light point when thedevice is in the colored state during daytime). A short is a localizedelectronically conductive pathway spanning the ion conducting layer(e.g., an electronically conductive pathway between the two TCO layers).A pinhole is a region where one or more layers of the electrochromicdevice are missing or damaged so that electrochromism is not exhibited.Pinholes are not electrical shorts. Three types of defects are ofprimary concern: (1) visible pinholes, (2) visible shorts, and (3)non-visible shorts. Typically, though not necessarily, a visible shortwill have defect dimension of at least about 3 micrometers resulting ina region, e.g. of about 1 cm in diameter, where the electrochromiceffect is perceptibly diminished—these regions can be reducedsignificantly by isolating the defect causing the visible short so thatto the naked eye the visible short will resemble only a visible pinhole.A visible pinhole will have a defect dimension of at least about 100micrometers.

In some cases, an electrical short is created by a conductive particlelodging in the ion conducting layer, thereby causing an electronic pathbetween the counter electrode layer and the electrochromic layer or theTCO associated with either one of them. In some other cases, a defect iscaused by a particle on the substrate (on which the electrochromic stackis fabricated) and such particle causes layer delamination (sometimescalled “pop-off”) or the layers not to adhere to the substrate. Bothtypes of defects are illustrated below in FIGS. 4 and 5A-5C. Adelamination or pop-off defect can lead to a short if it occurs before aTCO or associated EC or CE is deposited. In such cases, the subsequentlydeposited TCO or EC/CE layer will directly contact an underlying TCO orCE/EC layer providing direct electronic conductive pathway. A fewexamples of defect sources are presented in the table below. The tablebelow is intended to provide examples of mechanisms that lead to thedifferent types of visible and non-visible defects. Additional factorsexist which may influence how the EC window responds to a defect withinthe stack.

Particle Location Worst Case Failure Effect On float Pops off leavingpinhole Pinhole On TEC Pops off allowing ITO- Visible short TEC shortVoltage drop On EC Leakage across IC Visible short Voltage drop On ICPops off leaving pinhole Pinhole On CE Pops off leaving pinhole Pinhole

An electrical short, even a non-visible one, can cause leakage currentacross the ion conducting layer and result in a potential drop in thevicinity of the short. If the potential drop is of sufficient magnitudeit will prevent the electrochromic device from undergoing anelectrochromic transition in the vicinity of the short. In the case of avisible short the defect will appear as a light central region (when thedevice is in the colored state) with a diffuse boundary such that thedevice gradually darkens with distance from the center of the short. Ifthere are a significant number of electrical shorts (visible ornon-visible) concentrated in an area of an electrochromic device, theymay collectively impact a broad region of the device whereby the devicecannot switch in such region. This is because the potential differencebetween the EC and CE layers in such regions cannot attain a thresholdlevel required to drive ions across the ion conductive layer. In certainimplementations described herein, the shorts (both visible andnon-visible) are sufficiently well controlled that the leakage currentdoes not have this effect anywhere on the device. It should beunderstood that leakage current may result from sources other thanshort-type defects. Such other sources include broad-based leakageacross the ion conducting layer and edge defects such as roll offdefects as described elsewhere herein and scribe line defects. Theemphasis here is on leakage caused only by points of electrical shortingacross the ion conducting layer in the interior regions of theelectrochromic device.

FIG. 4 is a schematic cross-section of an electrochromic device 400 witha particle in the ion conducting layer causing a localized defect in thedevice. Electrochromic device 400 includes the same components asdepicted in FIG. 2 for electrochromic device 200. In the ion conductinglayer 208 of electrochromic device 400, however, there is a conductiveparticle 402 or other artifact causing a defect. Conductive particle 402results in a short between electrochromic layer 206 and counterelectrode layer 210. This short does not allow the flow of ions betweenelectrochromic layer 206 and counter electrode layer 210, insteadallowing electrons to pass locally between the layers, resulting in atransparent region 404 in the electrochromic layer 206 and a transparentregion 406 in the counter electrode layer 210 when the remainder oflayers 210 and 206 are in the colored state. That is, if electrochromicdevice 400 is in the colored state, conductive particle 402 rendersregions 404 and 406 of the electrochromic device unable to enter intothe colored state. Sometimes the defect regions are referred to as“constellations” because they appear as a series of bright spots (orstars) against a dark background (the remainder of the device being inthe colored state). Humans will naturally direct their attention to theconstellations and often find them distracting or unattractive.

FIG. 5A is a schematic cross-section of an electrochromic device 500with a particle 502 or other debris on conductive layer 204 prior todepositing the remainder of the electrochromic stack. Electrochromicdevice 500 includes the same components as electrochromic device 200.Particle 502 causes the layers in the electrochromic stack 220 to bulgein the region of particle 502, due to conformal layers 206-210 beingdeposited sequentially over particle 502 as depicted (in this example,layer 214 has not yet been deposited). While not wishing to be bound bya particular theory, it is believed that layering over such particles,given the relatively thin nature of the layers, can cause stress in thearea where the bulges are formed. More particularly, in each layer,around the perimeter of the bulged region, there can be defects in thelayer, e.g. in the lattice arrangement or on a more macroscopic level,cracks or voids. One consequence of these defects would be, for example,an electrical short between electrochromic layer 206 and counterelectrode layer 210 or loss of ion conductivity in layer 208. Thesedefects are not depicted in FIG. 5A, however.

Referring to FIG. 5B, another consequence of defects caused by particle502 is called a “pop-off.” In this example, prior to deposition ofconductive layer 214, a portion above the conductive layer 204 in theregion of particle 502 breaks loose, carrying with it portions ofelectrochromic layer 206, ion conducting layer 208, and counterelectrode layer 210. The “pop-off” is piece 504, which includes particle502, a portion of electrochromic layer 206, as well as ion conductinglayer 208 and counter electrode layer 210. The result is an exposed areaof conductive layer 204. Referring to FIG. 5C, after pop-off and onceconductive layer 214 is deposited, an electrical short is formed whereconductive layer 214 comes in contact with conductive layer 204. Thiselectrical short would leave a transparent region in electrochromicdevice 500 when it is in the colored state, similar in appearance to thedefect created by the short described above in relation to FIG. 4.

Pop-off defects due to particles or debris on substrate 202 or 204 (asdescribed above), on ion conducting layer 208, and on counterelectrodelayer 210 may also occur, causing pinhole defects when theelectrochromic device is in the colored state. Also, if particle 502 islarge enough and does not cause a pop-off, it might be visible whenelectrochromic device 500 is in the bleached state.

The electrochromic devices in certain embodiments are also scalable tosubstrates smaller or larger than architectural glass. An electrochromicstack can be deposited onto substrates that are a wide range of sizes,up to about 12 inches by 12 inches, or even 80 inches by 120 inches. Thecapability of manufacturing electrochromic devices of 20 by 20 inchesallows the manufacture of electrochromic architectural glass for manyapplications.

Even very small defects, ones that do not create noticeable points oflight or constellations, can cause serious performance problems. Forexample, small shorts, particularly multiple instances of them in arelatively small area, can cause a relatively large leakage current. Asa result, there may be a large local potential drop which prevents theelectrochromic device from switching in the vicinity of the leakagecurrent. Hence small defects can limit the scalability of electrochromicdevices and sometimes preclude deployment on architectural glass.

In one embodiment, the number of visible pinhole defects is no greaterthan about 0.04 per square centimeter. In another embodiment, the numberof visible pinhole defects is no greater than about 0.02 per squarecentimeter, and in more specific embodiments, the number of such defectsis no greater than about 0.01 per square centimeter. Typically, thevisible short-type defects are individually treated after fabrication toleave short-related pinholes as the only visible defects. In oneembodiment, the number of visible short-related pinhole defects is nogreater than about 0.005 per square centimeter. In another embodiment,the number of visible short-related pinhole defects is no greater thanabout 0.003 per square centimeter, and in more specific embodiments, thenumber of such defects is no greater than about 0.001 per squarecentimeter. In one embodiment, the total number of visible defects,pinholes and short-related pinholes created from isolating visibleshort-related defects, is less than about 0.1 defects per squarecentimeter, in another embodiment less than about 0.08 defects persquare centimeter, in another embodiment less than about 0.045 defectsper square centimeter (less than about 450 defects per square meter ofwindow).

In some embodiments, the number of non-visible electrical short defectsresults in leakage currents of less than about 5 μA/cm² at ±2V bias.These values apply across the entire face of the electrochromic device(i.e., there is no region of the device (anywhere on the device) havinga defect density greater than the recited value).

In some embodiments, the electrochromic device has no visible defectsgreater than about 1.6 mm in diameter (the largest transverse dimensionof the defect). In another embodiment, the device has no visible defectsgreater than about 0.5 mm in diameter, in another embodiment the devicehas no visible defects greater than about 100 μm in diameter.

In some embodiments, electrochromic glass is integrated into aninsulating glass unit (IGU). An insulating glass unit consists ofmultiple glass panes assembled into a unit, generally with the intentionof maximizing the thermal insulating properties of a gas contained inthe space formed by the unit while at the same time providing clearvision through the unit. Insulating glass units incorporatingelectrochromic glass would be similar to insulating glass unitscurrently known in the art, except for electrical leads for connectingthe electrochromic glass to voltage source. Due to the highertemperatures (due to absorption of radiant energy by an electrochromicglass) that electrochromic insulating glass units may experience, morerobust sealants than those used in conventional insulating glass unitsmay be necessary. For example, stainless steel spacer bars, hightemperature polyisobutylene (PIB), new secondary sealants, foil coatedPIB tape for spacer bar seams, and the like.

Method of Fabricating Electrochromic Windows

Deposition of the Electrochromic Stack

As mentioned in the summary above, one aspect of the disclosedembodiments is a method of fabricating an electrochromic window. In abroad sense, the method includes sequentially depositing on a substrate(i) an electrochromic layer, (ii) an ion conducting layer, and (iii) acounter electrode layer to form a stack in which the ion conductinglayer separates the electrochromic layer and the counter electrodelayer. The sequential deposition employs a single integrated depositionsystem having a controlled ambient environment in which the pressure,temperature, and/or gas composition are controlled independently of anexternal environment outside of the integrated deposition system, andthe substrate does not leave the integrated deposition system at anytime during the sequential deposition of the electrochromic layer, theion conducting layer, and the counter electrode layer. (Examples ofintegrated deposition systems which maintain controlled ambientenvironments are described in more detail below in relation to FIGS.8A-8E.) The gas composition may be characterized by the partialpressures of the various components in the controlled ambientenvironment. The controlled ambient environment also may becharacterized in terms of the number of particles or particle densities.In certain embodiments, the controlled ambient environment containsfewer than 350 particles (of size 0.1 micrometers or larger) per m³. Incertain embodiments, the controlled ambient environment meets therequirements of a class 100 clean room (US FED STD 209E). In certainembodiments, the controlled ambient environment meets the requirementsof a class 10 clean room (US FED STD 209E). The substrate may enterand/or leave the controlled ambient environment in a clean room meetingclass 100 or even class 10 requirements.

Typically, but not necessarily, this method of fabrication is integratedinto a multistep process for making an electrochromic window usingarchitectural glass as the substrate. For convenience, the followingdescription contemplates the method and its various embodiments in thecontext of a multistep process for fabricating an electrochromic window,but methods of the disclosed embodiments are not so limited.Electrochromic mirrors and other devices may be fabricated using some orall of the operations and approaches described herein.

FIG. 6A is a cross-sectional representation of an electrochromic windowdevice, 600, in accord with a multistep process such as that describedin relation to FIG. 7A. FIG. 7A depicts a process flow describing amethod, 700, of fabricating an electrochromic window which incorporateselectrochromic device 600. FIG. 6B is a top view of device 600 showingthe location of trenches cut into the device. Thus, FIGS. 6A-B and 7Awill be described together. One aspect of the description is anelectrochromic window including device 600 and another aspect of thedescription is a method, 700, of fabricating an electrochromic windowwhich includes device 600. Included in the following description aredescriptions of FIGS. 7B-7E. FIGS. 7B-7D depict specific methods offabricating an electrochromic stack which is part of device 600. FIG. 7Edepicts a process flow for a conditioning process used in fabricating,e.g., device 600.

FIG. 6A shows a specific example of an electrochromic device, 600, whichis fabricated starting with a substrate made of glass 605 whichoptionally has a diffusion barrier 610 coating and a first transparentconducting oxide (TCO) coating 615 on the diffusion barrier. Method 700employs a substrate that is, for example, float glass with sodiumdiffusion barrier and antireflective layers followed by a transparentconductive layer, for example a transparent conductive oxide 615. Asmentioned above, substrates suitable for devices in certain embodimentsinclude glasses sold under the trademarks TEC Glass® by Pilkington ofToledo, Ohio, and SUNGATE® 300 and SUNGATE® 500 by PPG Industries, ofPittsburgh, Pa. The first TCO layer 615 is the first of two conductivelayers used to form the electrodes of electrochromic device 600fabricated on the substrate.

Method 700 begins with a cleaning process, 705, where the substrate iscleaned to prepare it for subsequent processing. As mentioned above, itis important to remove contaminants from the substrate because they cancause defects in the device fabricated on the substrate. One criticaldefect is a particle or other contaminant that creates a conductivepathway across the IC layer and thus shorts the device locally causingvisually discernable anomalies in the electrochromic window. One exampleof a cleaning process and apparatus suitable for the fabrication methodsherein is Lisec™ (a trade name for a glass washing apparatus and processavailable from (LISEC Maschinenbau Gmbh of Seitenstetten, Austria).

Cleaning the substrate may include mechanical scrubbing as well asultrasonic conditioning to remove unwanted particulates. As mentioned,particulates may lead to cosmetic flaws as well as local shorting withinthe device.

Once the substrate is cleaned, a first laser scribe process, 710, isperformed in order to remove a line of the first TCO layer on thesubstrate. In one embodiment, the resulting trench ablates through boththe TCO and the diffusion barrier (although in some cases the diffusionbarrier is not substantially penetrated). FIG. 6A depicts this firstlaser scribe trench, 620. A trench is scribed in the substrate acrossthe entire length of one side of the substrate in order to isolate anarea of the TCO, near one edge of the substrate, which will ultimatelymake contact with a first bus bar, 640, used to provide current to asecond TCO layer, 630, which is deposited on top of electrochromic (EC)stack 625 (which includes the electrochromic, ion conducting and counterelectrode layers as described above). FIG. 6B shows schematically (notto scale) the location of trench 620. In the depicted embodiment, thenon-isolated (main) portion of the first TCO layer, on the diffusionbarrier, ultimately makes contact with a second bus bar, 645. Isolationtrench 620 may be needed because, in certain embodiments, the method ofattaching the first bus bar to the device includes pressing it throughthe device stack layers after they are laid down (both on the isolatedportion of the first TCO layer and the main portion of the first TCOlayer). Those of skill in the art will recognize that other arrangementsare possible for providing current to the electrodes, in this case TCOlayers, in the electrochromic device. The TCO area isolated by the firstlaser scribe is typically an area along one edge of the substrate thatwill ultimately, along with the bus bars, be hidden when incorporatedinto the integrated glass unit (IGU) and/or window pane, frame orcurtain wall. The laser or lasers used for the first laser scribe aretypically, but not necessarily, pulse-type lasers, for examplediode-pumped solid state lasers. For example, the laser scribes can beperformed using a suitable laser from IPG Photonics (of Oxford Mass.),or from Ekspla (of Vilnius Lithuania).

The laser trench is dug along a side of the substrate from end to end toisolate a portion of the first TCO layer; the depth and width dimensionsof trench 620 made via first laser scribe 710 should be sufficient toisolate the first TCO layer from the bulk TCO once the device issubsequently deposited. The depth and width of the trench should besufficient to prevent any remaining particulates to short across thetrench. In one embodiment, the trench is between about 300 nm and 500 nmdeep and between about 20 μm and 50 μm wide. In another embodiment, thetrench is between about 350 nm and 450 nm deep and between about 30 μmand 45 μm wide. In another embodiment, the trench is about 400 nm deepand about 40 μm wide.

After the first laser scribe 710, the substrate is cleaned again(operation 715), typically but not necessarily, using cleaning methodsdescribed above. This second cleaning process is performed to remove anydebris caused by the first laser scribe. Once cleaning operation 715 iscomplete, the substrate is ready for deposition of EC stack 625. This isdepicted in process flow 700 as process 720. As mentioned above, themethod includes sequentially depositing on a substrate (i) an EC layer,(ii) an IC layer, and (iii) a CE layer to form a stack in which the IClayer separates the EC layer and the CE layer using a single integrateddeposition system having a controlled ambient environment in which thepressure and/or gas composition are controlled independently of anexternal environment outside of the integrated deposition system, andthe substrate does not leave the integrated deposition system at anytime during the sequential deposition of the EC layer, the IC layer, andthe CE layer. In one embodiment, each of the sequentially depositedlayers is physical vapor deposited. In general the layers of theelectrochromic device may be deposited by various techniques includingphysical vapor deposition, chemical vapor deposition, plasma enhancedchemical vapor deposition, and atomic layer deposition, to name a few.The term physical vapor deposition as used herein includes the fullrange of art understood PVD techniques including sputtering,evaporation, ablation, and the like. FIG. 7B depicts one embodiment ofprocess 720. First the EC layer is deposited on the substrate, process722, then the IC layer is deposited, process 724, then the CE layer,process 726. The reverse order of deposition is also an embodiment, thatis, where the CE layer is deposited first, then the IC layer and thenthe EC layer. In one embodiment, each of the electrochromic layer, theion conducting layer, and the counter electrode layer is a solid phaselayer. In another embodiment, each of the electrochromic layer, the ionconducting layer, and the counter electrode layer includes onlyinorganic material.

It should be understood that while certain embodiments are described interms of a counter electrode layer, an ion conductor layer, and anelectrochromic layer, any one or more of these layers may be composed ofone or more sub-layers, which may have distinct compositions, sizes,morphologies, charge densities, optical properties, etc. Further any oneor more of the device layers may have a graded composition or a gradedmorphology in which the composition or morphology, respectively, changesover at least a portion of the thickness of the layer. In one example,the concentration of a dopant or charge carrier varies within a givenlayer, at least as the layer is fabricated. In another example, themorphology of a layer varies from crystalline to amorphous. Such gradedcomposition or morphology may be chosen to impact the functionalproperties of the device. In some cases, additional layers may be addedto the stack. In one example a heat spreader layer is interposed betweenone or both TCO layers and the EC stack.

In another example, a cathodically coloring electrochromic layer and/oran anodically coloring counter electrode layer may be deposited as twodistinct sub-layers optionally having different compositions, althoughboth sub-layers may have compositions (e.g., compositions that includeelectrochromic materials or compositions that include counter electrodematerials) as generally described herein. Certain processing steps(e.g., lithiation) may occur between depositing the sub-layers. In aparticular embodiment, counter electrode material is deposited in twosub-layers having different compositions. The first sub-layer (closer tothe cathodically coloring electrochromic layer) may be anodicallycoloring, while the second sub-layer (farther away from the cathodicallycoloring electrochromic layer) may or may not be anodically coloring, ormay be more weakly anodically coloring than the first sub-layer. Betweendeposition of the first and second sub-layers, the partially fabricateddevice may be subject to a lithiation operation. The second sub-layermay reduce the risk of forming defects. In some cases the secondsub-layer acts as a defect-mitigating layer, and may be moreelectronically insulating than the first sub-layer. A further discussionof defect-mitigating layers and their properties is provided in U.S.patent application Ser. No. 13/763,505, filed Feb. 8, 2013, and titled“DEFECT-MITIGATION LAYERS IN ELECTROCHROMIC DEVICES,” which isincorporated herein by reference in its entirety.

Also, as described above, various electrochromic devices utilize ionmovement between the electrochromic layer and the counter electrodelayer via an ion conducting layer. In some embodiments these ions (orneutral precursors thereof) are introduced to the stack as one or morelayers (as described below in more detail in relation to FIGS. 7C and7D) that eventually intercalate into the stack. In some embodimentsthese ions are introduced into the stack concurrently with one or moreof the electrochromic layer, the ion conducting layer, and the counterelectrode layer. In one embodiment, where lithium ions are used, lithiumis, e.g., sputtered along with the material used to make the one or moreof the stack layers or sputtered as part of a material that includeslithium (e.g., by a method employing lithium nickel tungsten oxide,optionally provided with other additives as listed herein). In oneembodiment, the IC layer is deposited via sputtering a lithium siliconaluminum oxide target. In another embodiment, the Li is cosputteredalong with silicon aluminum in order to achieve the desired film.

Referring again to process 722 in FIG. 7B, in one embodiment, depositingthe electrochromic layer comprises depositing WO_(x), e.g. where x isless than 3.0 and at least about 2.7. In this embodiment, the WO_(x) hasa substantially nanocrystalline morphology. In some embodiments, theelectrochromic layer is deposited to a thickness of between about 200 nmand 700 nm. In one embodiment, depositing the electrochromic layerincludes sputtering tungsten from a tungsten containing target. In onesuch embodiment, a metallic tungsten (or tungsten alloy) target is used.In another embodiment (which may also employ a metallic tungsten target)the sputter gas is an inert gas (e.g., argon or xenon) with some oxygencontaining gas (e.g., molecular or atomic oxygen) present. This is partof the controlled ambient environment that may be present in adeposition chamber or a station within a larger chamber. In oneembodiment, the gas composition contains between about 30% and about100% oxygen, in another embodiment between about 50% and about 80%oxygen, in yet another embodiment between about 65% and about 75%oxygen. In one embodiment, the tungsten containing target containsbetween about 80% and 100% (by weight) tungsten, in another embodimentbetween about 95% and 100% tungsten, and in yet another embodimentbetween about 99% and 100% tungsten. In one embodiment, the gascomposition is about 70% oxygen/30% argon and the target is metallictungsten of a purity of between about 99% and 100%. In anotherembodiment a tungsten oxide W(O) ceramic target is sputtered with, e.g.,argon. The pressure in the deposition station or chamber, in oneembodiment, is between about 1 and about 75 mTorr, in another embodimentbetween about 5 and about 50 mTorr, in another embodiment between about10 and about 20 mTorr. In one embodiment, the substrate temperature forprocess 722 is between about 100° C. and about 500° C., in anotherembodiment between about 100° C. and about 300° C., and in anotherembodiment between about 150° C. and about 250° C. The substratetemperature may be measured in situ by, e.g., a thermocouple such as aninfra-red thermo-couple (IR t/c). In one embodiment, the power densityused to sputter the EC target is between about 2 Watts/cm² and about 50Watts/cm² (determined based on the power applied divided by the surfacearea of the target); in another embodiment between about 10 Watts/cm²and about 20 Watts/cm²; and in yet another embodiment between about 15Watts/cm² and about 20 Watts/cm². In some embodiments, the powerdelivered to effect sputtering is provided via direct current (DC). Inother embodiments, pulsed DC/AC reactive sputtering is used. In oneembodiment, where pulsed DC/AC reactive sputtering is used, thefrequency is between about 20 kHz and about 400 kHz, in anotherembodiment between about 20 kHz and about 50 kHz, in yet anotherembodiment between about 40 kHz and about 50 kHz, in another embodimentabout 40 kHz. The above conditions may be used in any combination withone another to effect deposition of a high quality tungsten oxideelectrochromic layer.

In one embodiment, in order to normalize the rate of deposition oftungsten, multiple targets are used so as to obviate the need forinappropriately high power (or other inappropriate adjustment to desiredprocess conditions) to increase deposition rate. The distance betweenthe target and the substrate may also be important. In one embodiment,the distance between the target (cathode or source) to the substratesurface is between about 35 mm and about 150 mm; in another embodimentbetween about 45 mm and about 130 mm; and in another embodiment betweenabout 70 mm and about 100 mm.

It should be understood that while deposition of the EC layer isdescribed in terms of sputtering from a target, other depositiontechniques are employed in some embodiments. For example, chemical vapordeposition, atomic layer deposition, and the like may be employed. Eachof these techniques, along with PVD, has its own form of material sourceas is known to those of skill in the art.

Referring again to FIG. 7B, operation 724, once the EC layer isdeposited, the IC layer is deposited. In one embodiment, depositing theion conducting layer includes depositing a material selected from thegroup consisting of a tungsten oxide, a tantalum oxide, a niobium oxide,and a silicon aluminum oxide. In another embodiment, depositing the ionconducting layer includes sputtering a target including between about 2%and 20% by weight of aluminum (remainder silicon) in an oxygencontaining environment to produce a layer of silicon aluminum oxide. Ina more specific embodiment, the target is between about 5% and about 10%aluminum in silicon, in another embodiment, between about 7% and about9% aluminum in silicon. In one embodiment, the gas composition containsbetween about 15% and about 70% oxygen, in another embodiment betweenabout 20% and about 50% oxygen, in yet another embodiment between about25% and about 45% oxygen, in another embodiment about 35% oxygen. Inanother embodiment, depositing the ion conducting layer includesdepositing the ion conducting layer to a thickness of between about 10and 100 nm. In yet another embodiment, depositing the ion conductinglayer includes depositing the ion conducting layer to a thickness ofbetween about 20 and 50 nm. In one embodiment, the power density used tosputter the IC target is between about 1 Watts/cm² and about 20Watts/cm² (determined based on the power applied divided by the surfacearea of the target); in another embodiment between about 5 Watts/cm² andabout 7 Watts/cm²; and in yet another embodiment between about 6Watts/cm² and about 6.5 Watts/cm². In some embodiments, the powerdelivered to effect sputtering is provided via direct current (DC). Inother embodiments, pulsed DC/AC reactive sputtering is used. In oneembodiment, where pulsed DC/AC reactive sputtering is used, thefrequency is between about 20 kHz and about 400 kHz, in anotherembodiment between about 20 kHz and about 50 kHz, in yet anotherembodiment between about 40 kHz and about 50 kHz, in another embodimentabout 40 kHz. The pressure in the deposition station or chamber, in oneembodiment, is between about 5 mTorr and about 40 mTorr, in anotherembodiment between about 10 mTorr and about 30 mTorr, in anotherembodiment about 20 mTorr. In one embodiment, the substrate temperatureranges for operation 724 are between about 20° C. and about 200° C., insome embodiments between about 20° C. and about 150° C., and it yetstill other embodiments between about 25° C. and about 100° C. The aboveconditions may be used in any combination with one another to effectdeposition of a high quality ion conducting layer.

Referring again to FIG. 7B, operation 726, after the IC layer isdeposited, the CE layer is deposited. In one embodiment, depositing thecounter electrode layer includes depositing a layer of nickel tungstenoxide (NiWO) that optionally includes one or more additives and/orhalogens as described above, preferably amorphous NiWO. In a specificembodiment, depositing the counter electrode layer includes sputtering atarget including about 30% (by weight) to about 70% of tungsten innickel in an oxygen containing environment to produce a layer of nickeltungsten oxide. In another embodiment the target is between about 40%and about 60% tungsten in nickel, in another embodiment between about45% and about 55% tungsten in nickel, and in yet another embodimentabout 51% tungsten in nickel. In one embodiment, the gas compositioncontains between about 30% and about 100% oxygen, in another embodimentbetween about 80% and about 100% oxygen, in yet another embodimentbetween about 95% and about 100% oxygen, in another embodiment about100% oxygen. The additive(s) may be introduced via the sputter target insome cases. In these or other cases, the additive(s) may be introducedvia another method, for example through evaporation, which may or maynot occur concurrently with sputtering.

In one embodiment, the power density used to sputter the CE target isbetween about 2 Watts/cm² and about 50 Watts/cm² (determined based onthe power applied divided by the surface area of the target); in anotherembodiment between about 5 Watts/cm² and about 20 Watts/cm²; and in yetanother embodiment between about 8 Watts/cm² and about 10 Watts/cm², inanother embodiment about 8 Watts/cm². In some embodiments, the powerdelivered to effect sputtering is provided via direct current (DC). Inother embodiments, pulsed DC/AC reactive sputtering is used. In oneembodiment, where pulsed DC/AC reactive sputtering is used, thefrequency is between about 20 kHz and about 400 kHz, in anotherembodiment between about 20 kHz and about 50 kHz, in yet anotherembodiment between about 40 kHz and about 50 kHz, in another embodimentabout 40 kHz. The pressure in the deposition station or chamber, in oneembodiment, is between about 1 and about 50 mTorr, in another embodimentbetween about 20 and about 40 mTorr, in another embodiment between about25 and about 35 mTorr, in another embodiment about 30 mTorr.

In some cases, a nickel tungsten oxide NiWO ceramic target (which may ormay not include one or more additives as described above) is sputteredwith, e.g., argon and oxygen. In one embodiment, the NiWO is betweenabout 15% (atomic) Ni and about 60% Ni; between about 10% W and about40% W; and between about 30% O and about 75% O. In another embodiment,the NiWO is between about 30% (atomic) Ni and about 45% Ni; betweenabout 10% W and about 25% W; and between about 35% O and about 50% O. Inone embodiment, the NiWO is about 42% (atomic) Ni, about 14% W, andabout 44% O. As noted, the NiWO target may also include one or more ofthe additives and/or halogens listed above. In another embodiment,depositing the counter electrode layer includes depositing the counterelectrode layer to a thickness of between about 150 and 350 nm; in yetanother embodiment between about 200 and about 250 nm thick. The aboveconditions may be used in any combination with one another to effectdeposition of a high quality NiWO layer that optionally includes one ormore additional additives and/or halogens. The above conditions may alsobe used in any combination with one another to effect deposition of acounter electrode layer having a different composition, for example onethat includes a base anodically coloring electrochromic material and oneor more additives as described above. Although much of the descriptionfocuses on embodiments where the base anodically coloring material isnickel oxide and the additive is or includes tungsten, other materialsmay also be used. Details herein regarding nickel in the counterelectrode may also apply to other metals used in a base anodicallycoloring material. Details herein regarding tungsten in the counterelectrode may also apply to other additives, alone or in combination, aslisted herein.

In another embodiment, operation 726 of FIG. 7B includes depositing acounter electrode layer including at least one base anodically coloringelectrochromic material containing at least one metal selected from thegroup consisting of chromium, manganese, iron, cobalt, nickel, rhodium,ruthenium, vanadium, and iridium, or selected from the group consistingof chromium, manganese, iron, cobalt, nickel, rhodium, and iridium, orselected from the group consisting of nickel and iridium. The metal maybe provided as an oxide. Where the CE layer is deposited throughsputtering, the sputter target may include one or more metals (or oxidesthereof) selected from the group consisting of chromium, manganese,iron, cobalt, nickel, rhodium, ruthenium, vanadium, and iridium, or fromthe group consisting of chromium, manganese, iron, cobalt, nickel,rhodium, and iridium, or from the group consisting of nickel andiridium. In these or other cases, depositing the counter electrode layermay include depositing one or more additives/additional materials aspart of the layer. The additive material may be selected from the groupconsisting of silver (Ag), arsenic (As), gold (Au), boron (B), cadmium(Cd), cesium (Cs), copper (Cu), europium (Eu), gallium (Ga), gadolinium(Gd), germanium (Ge), mercury (Hg), osmium (Os), lead (Pb), palladium(Pd), promethium (Pm), polonium (Po), platinum (Pt), radium (Ra),rubidium (Rb), terbium (Tb), technetium (Tc), thorium (Th), and thallium(Tl), or from any of the sub-groups identified herein. For instance, incertain cases the additional material is selected from the groupconsisting of germanium, gadolinium, gallium and copper, or the groupconsisting of germanium, gadolinium and gallium, or the group consistingof germanium and copper. The additional material may be provided throughsputtering, for example with a sputter target including one or more ofthe additional materials, or an oxide of one or more of the additionalmaterials.

The sputtering process for forming the CE layer may utilize one or moresputter targets. Where one sputter target is used, it may include boththe anodically coloring electrochromic material and the additive (eitheror both provided in oxide form on the target). The sputter target mayinclude a grid or other overlapping shape where different portions ofthe grid include the different relevant materials. In other cases, thesputter target may be an alloy of the relevant materials. Where twosputter targets are used, each sputter target may include one of therelevant materials (e.g., the anodically coloring electrochromicmaterial or the additive, either or both in oxide form). The sputtertargets may overlap in some cases. As noted, the counter electrode layeris typically an oxide material. Oxygen may be provided as a part of thesputter target. In other cases, the sputter targets are substantiallypure metals, and sputtering is done in the presence of oxygen to formthe oxide.

In one embodiment, in order to normalize the rate of deposition of theCE layer, multiple targets are used so as to obviate the need forinappropriately high power (or other inappropriate adjustment to desiredprocess conditions) to increase deposition rate. In one embodiment, thedistance between the CE target (cathode or source) to the substratesurface is between about 35 mm and about 150 mm; in another embodimentbetween about 45 mm and about 130 mm; and in another embodiment betweenabout 70 mm and about 100 mm.

It should be understood that while the order of deposition operations isdepicted in FIG. 7B (and implied in FIG. 6A) to be first EC layer,second IC layer, and finally CE layer, the order can be reversed invarious embodiments. In other words, when as described herein“sequential” deposition of the stack layers is recited, it is intendedto cover the following “reverse” sequence, first CE layer, second IClayer, and third EC layer, as well the “forward” sequence describedabove. Both the forward and reverse sequences can function as reliablehigh-quality electrochromic devices. Further, it should be understoodthat conditions recited for depositing the various EC, IC, and CEmaterials recited here, are not limited to depositing such materials.Other materials may, in some cases, be deposited under the same orsimilar conditions. Further, non-sputtering deposition conditions may beemployed in some embodiments to create the same or similar depositedmaterials as those described in the context of FIGS. 6A-6B and FIGS.7A-7E.

Since the amount of charge each of the EC and the CE layers can safelyhold varies, depending on the material used, the relative thickness ofeach of the layers may be controlled to match capacity as appropriate.In one embodiment, the electrochromic layer includes tungsten oxide andthe counter electrode includes nickel tungsten oxide (with one or moreadditives as described herein), and the ratio of thicknesses of theelectrochromic layer to the counter electrode layer is between about1.7:1 and 2.3:1, or between about 1.9:1 and 2.1:1 (with about 2:1 beinga specific example). Such thickness ratios may also be used where thecounter electrode is made of a different material.

Referring again to FIG. 7B, operation 720, after the CE layer isdeposited, the EC stack is complete. It should be noted that in FIG. 7A,process operation 720 which refers to “depositing stack” means in thiscontext, the EC stack plus the second TCO layer (sometimes referred toas the “ITO” when indium tin oxide is used to make the second TCO).Generally “stack” in this description refers to the EC-IC-CE layers;that is, the “EC stack.” Referring again to FIG. 7B, in one embodiment,represented by process 728, a TCO layer is deposited on the stack.Referring to FIG. 6A, this would correspond to second TCO layer 630 onEC stack 625. Process flow 720 is finished once process 728 is complete.Typically, but not necessarily, a capping layer is deposited on the ECstack. In some embodiments, the capping layer is SiAlO, similar to theIC layer. In some embodiments, the capping layer is deposited bysputtering, similar to the conditions under which the IC layer isdeposited. The thickness of a capping layer is typically about 30 nm to100 nm. In one embodiment, depositing the layer of transparentconductive oxide is performed under conditions whereby the transparentconductive oxide has a sheet resistance of between about 10 and 30ohms/square. In one embodiment as discussed above, the first and secondTCO layers are of matched sheet resistance for optimum efficiency of theelectrochromic device. Ideally the first TCO layer's morphology shouldbe smooth for better conformal layers in the deposited stack. In oneembodiment, a substantially uniform TCO layer varies only about ±10% ineach of the aforementioned thickness ranges. In another embodiment, asubstantially uniform TCO layer varies only about ±5% in each of theaforementioned thickness ranges. In another embodiment, a substantiallyuniform TCO layer varies only about ±2% in each of the aforementionedthickness ranges.

In certain specific embodiments, the second TCO layer 630 is depositedusing some or all of the following conditions. The recited conditionsmay be employed to form a thin, low-defect layer of indium tin oxide bysputtering a target containing indium oxide in tin oxide, e.g. with anargon sputter gas with or without oxygen. In one embodiment, thethickness of the TCO layer is between about 5 nm and about 10,000 nm, inanother embodiment between about 10 nm and about 1,000 nm. In yetanother embodiment this thickness is between about 10 nm and about 500nm. In one embodiment, the substrate temperature for operation 728 isbetween about 20 and about 300° C., in another embodiment between about20 and about 250° C., and in another embodiment between about 80 andabout 225° C. In one embodiment, depositing the TCO layer includessputtering a target including between about 80% (by weight) to about 99%of In₂O₃ and between about 1% and about 20% SnO₂ using an inert gas,optionally with oxygen. In a more specific embodiment, the target isbetween about 85% (by weight) to about 97% of In₂O₃ and between about 3%and about 15% SnO₂. In another embodiment, the target is about 90% ofIn₂O₃ and about 10% SnO₂. In one embodiment, the gas compositioncontains between about 0.1% and about 3% oxygen, in another embodimentbetween about 0.5% and about 2% oxygen, in yet another embodimentbetween about 1% and about 1.5% oxygen, in another embodiment about 1.2%oxygen. In one embodiment, the power density used to sputter the TCOtarget is between about 0.5 Watts/cm² and about 10 Watts/cm² (determinedbased on the power applied divided by the surface area of the target);in another embodiment between about 0.5 Watts/cm² and about 2 Watts/cm²;and in yet another embodiment between about 0.5 Watts/cm² and about 1Watts/cm², in another embodiment about 0.7 Watts/cm². In someembodiments, the power delivered to effect sputtering is provided viadirect current (DC). In other embodiments, pulsed DC/AC reactivesputtering is used. In one embodiment, where pulsed DC/AC reactivesputtering is used, the frequency is between about 20 kHz and about 400kHz, in another embodiment between about 50 kHz and about 100 kHz, inyet another embodiment between about 60 kHz and about 90 kHz, in anotherembodiment about 80 kHz. The pressure in the deposition station orchamber, in one embodiment, is between about 1 and about 10 mTorr, inanother embodiment between about 2 and about 5 mTorr, in anotherembodiment between about 3 and about 4 mTorr, in another embodimentabout 3.5 mTorr. In one embodiment, the indium tin oxide layer isbetween about 20% (atomic) In and about 40% In; between about 2.5% Snand about 12.5% Sn; and between about 50% O and about 70% O; in anotherembodiment, between about 25% In and about 35% In; between about 5.5% Snand about 8.5% Sn; and between about 55% O and about 65% O; and inanother embodiment, about 30% In, about 8% Sn; and about 62% O. Theabove conditions may be used in any combination with one another toeffect deposition of a high quality indium tin oxide layer.

As mentioned, the EC stack is fabricated in an integrated depositionsystem where the substrate does not leave the integrated depositionsystem at any time during fabrication of the stack. In one embodiment,the second TCO layer is also formed using the integrated depositionsystem where the substrate does not leave the integrated depositionsystem during deposition of the EC stack and the TCO layer. In oneembodiment, all of the layers are deposited in the integrated depositionsystem where the substrate does not leave the integrated depositionsystem during deposition; that is, in one embodiment the substrate is aglass sheet and a stack including the EC layer, the IC layer and the CElayer, sandwiched between a first and a second TCO layer, is fabricatedon the glass where the glass does not leave the integrated depositionsystem during deposition. In another implementation of this embodiment,the substrate is glass with a diffusion barrier deposited prior to entryin the integrated deposition system. In another implementation thesubstrate is glass and the diffusion barrier, a stack including the EClayer, the IC layer and the CE layer, sandwiched between a first and asecond TCO layer, are all deposited on the glass where the glass doesnot leave the integrated deposition system during deposition.

While not wishing to be bound by theory, it is believed that prior artelectrochromic devices suffered from high defectivity for variousreasons, one of which is the integration of unacceptably high numbers ofparticles into the IC layer during fabrication. Care was not taken toensure that each of the EC layer, IC layer, and CE layer were depositedin a single integrated deposition apparatus under a controlled ambientenvironment. In one process, the IC layer is deposited by a sol gelprocess, which is necessarily performed apart from other vacuumintegrated processes. In such process, even if the EC layer and/or theCE layer are deposited in a controlled ambient environment, therebypromoting high quality layers, the substrate would have to be removedfrom the controlled ambient environment to deposit the IC layer. Thiswould normally involve passing the substrate through a load lock (fromvacuum or other controlled ambient environment to an externalenvironment) prior to formation of the IC layer. Passage through a loadlock typically introduces numerous particles onto the substrate.Introducing such particles immediately before the IC layer is depositedgreatly increases the likelihood that defects will form in the criticalIC layer. Such defects lead to bright spots or constellations asdiscussed above.

As mentioned above, lithium may be provided with the EC, CE and/or IClayers as they are formed on the substrate. This may involve, forexample, co-sputtering of lithium together with the other materials of agiven layer (e.g., tungsten and oxygen). In certain embodimentsdescribed below the lithium is delivered via a separate process andallowed to diffuse or otherwise incorporate into the EC, CE and/or IClayers.

In some embodiments, the electrochromic stack includes a counterelectrode layer in direct physical contact with an electrochromic layer,without an ion conducting layer in between. The electrochromic and/orcounter electrode layer may include an oxygen-rich portion in contactwith the other of these layers. The oxygen-rich portion includes theelectrochromic material or counter electrode material, with a higherconcentration of oxygen than in the remaining portion of theelectrochromic layer and/or counter electrode layer. Electrochromicdevices fabricated according to such a design are further discussed anddescribed in U.S. Pat. No. 8,300,298, filed Apr. 30, 2010, which isherein incorporated by reference in its entirety.

Direct Lithiation of the Electrochromic Stack

In some embodiments, as mentioned above, intercalation of lithium ionsis responsible for switching the optical state of an electrochromicdevice stack. It should be understood that the needed lithium may beintroduced to the stack by various means. For example, lithium may beprovided to one or more of these layers concurrently with the depositionof the material of the layer (e.g., concurrent deposition of lithium andtungsten oxide during formation of the EC layer). In some cases,however, the process of FIG. 7B may be punctuated with one or moreoperations for delivering lithium to the EC layer, the IC layer, and/orthe CE layer. For example, lithium may also be introduced via one ormore separate lithiation steps in which elemental lithium is deliveredwithout substantial deposition of other material. Such lithiationstep(s) may take place after deposition of the EC layer, the IC layer,and/or the CE layer. Alternatively (or in addition), one or morelithiation steps may take intermediate between steps performed todeposit a single layer. For example, a counter electrode layer may bedeposited by first depositing a limited amount of counter electrodematerial, followed by directly depositing lithium, and then concluded bydepositing additional counter electrode material. Such approaches mayhave certain advantages such as better separating the lithium from theITO (or other material of a conductive layer) which improves adhesionand prevents undesirable side reactions. One example of a stackformation process employing a separate lithiation operation is presentedin FIG. 7C. In certain cases, the lithiation operation(s) takes placeduring while the deposition of a given layer is temporarily halted toallow lithium to be introduced before deposition of the layer iscompleted.

FIG. 7C depicts a process flow, 720 a, for depositing the stack onto asubstrate in a manner analogous to process 720 of FIG. 7A. Process flow720 a includes depositing an EC layer, operation 722, depositing an IClayer, operation 724, and depositing a CE layer, operation 726, asdescribed in relation to FIG. 7B. However, process flow 720 a differsfrom 720 by the addition of lithiation operations 723 and 727. In oneembodiment, the lithium is physical vapor deposited using an integrateddeposition system where the substrate does not leave the integrateddeposition system at any time during the sequential deposition of theelectrochromic layer, the ion conducting layer, the counter electrodelayer, and the lithium.

In certain embodiments, lithium is deposited using a high voltagelithium cathode since there are not many secondary electron emissionsduring lithium sputtering. In some embodiments, the power delivered toeffect sputtering is provided via direct current (DC). In otherembodiments, pulsed DC/AC reactive sputtering is used. In oneembodiment, where pulsed DC/AC reactive sputtering is used, thefrequency is between about 20 kHz and about 400 kHz, in anotherembodiment between about 100 kHz and about 300 kHz, in yet anotherembodiment between about 200 kHz and about 250 kHz, in anotherembodiment about 220 kHz. A lithium target is used. In one embodimentthe target is between about 80% (by weight) and 100% Li, in anotherembodiment between about 90% and about 99% Li, in another embodimentabout 99% Li. Typically, due to the extreme reactivity of elementallithium, lithiation is performed in an inert environment (e.g., argonalone). The power density used to sputter the lithium target is betweenabout 1 Watts/cm² and about 10 Watts/cm² (determined based on thedeposition surface area of the substrate); in another embodiment betweenabout 2 Watts/cm² and about 4 Watts/cm²; in yet another embodimentbetween about 2.5 Watts/cm² and about 3 Watts/cm²; in another embodimentabout 2.7 Watts/cm². In one embodiment the lithium sputtering is done ata pressure of between about 1 and about 20 mTorr, in another embodimentbetween about 5 and about 15 mTorr, in another embodiment about 10mTorr. The above conditions may be used in any combination with oneanother to effect deposition of a high quality lithiation process.

In one embodiment, lithium is deposited on both the EC layer and the CElayer as depicted in dual lithiation process 720 a. After the EC layeris deposited as described above, operation 722, lithium is sputtered onthe EC layer; see operation 723. Thereafter, the IC layer is deposited,operation 724, followed by the CE layer, operation 726. Then lithium isdeposited on the CE layer; see operation 727. In one embodiment where,e.g., the EC layer is tungsten oxide and about twice as thick as a CElayer, the total amount of lithium added to the stack is proportionedbetween the EC layer and the CE layer in a ratio of about 1:3 to 2:3;that is, the EC layer is sputtered with ⅓ of the total lithium and theCE layer with about ⅔ of the total lithium added to the stack. In aspecific embodiment, the lithium added to the stack is proportionedbetween the EC layer and the CE layer in a ratio of about 1:2.

In the depicted dual lithiation method, both the EC layer and the CElayer are lithiated. Without wishing to be bound by theory, it isbelieved that by delivering lithium to both the EC layer and the CElayer, performance and yield are improved. The relatively large volumechange due to insertion of lithium ions into a depleted layer (asfabricate) during initial equilibration (from a single lithiation on oneside of the IC layer) is avoided. These volume changes, which arereported to be as large as 6% in electrochromically active tungstenoxide initially devoid of lithium, can produce cracking and delaminationof the stack layers. Therefore, improvements can be realized byfabricating the stack with a dual lithiation process as describedherein, which results in less than 6% volume change in theelectrochromic layer. In certain embodiments, the volume change is atmost about 4%.

In one embodiment of the dual lithiation method, as explained above, theEC layer is treated with sufficient lithium to satisfy the requirementsof the EC material irreversibly bound lithium (to, e.g., compensate“blind charge”). The lithium needed for reversible cycling is added tothe CE layer (which also may have a blind charge). In certainembodiments, the lithium needed to compensate the blind charge can betitrated by monitoring optical density of the EC layer as lithium isadded since the EC layer will not substantially change color untilsufficient lithium has been added to fully compensate the blind charge.

One of ordinary skill in the art would appreciate that because metalliclithium is pyrophoric, i.e. highly reactive with moisture and oxygen,that lithiation methods described herein where lithium might be exposedto oxygen or moisture are performed either under vacuum, inertatmosphere or both. The controlled ambient environment of apparatus andmethods herein provides flexibility in lithium depositions, particularlywhere there are multiple lithiation steps. For example, where lithiationis performed in a titration process and/or among multiple steps in astack layering, the lithium can be protected from exposure to oxygen ormoisture.

In certain embodiments, the lithiation is performed at a rate sufficientto prevent formation of a substantial thickness of free lithium on theEC layer surface. In one embodiment, during lithiation of the EC layer,lithium targets are spaced sufficiently to give time for lithium todiffuse into the EC layer. Optionally, the substrate (and hence the EClayer) is heated to between about 100° C. and about 150° C. to enhancediffusion of lithium into the EC layer. Heating may be done separatelyor in combination with target spacing and substrate translation past thetarget(s). In some cases, the substrate is moved back and forth in frontof a sputtered lithium target in order to slow the delivery of lithiumto the substrate and prevent accumulation of free metallic lithium onthe stack surface.

In some cases, the lithiation processes are performed with isolationprotocols in place. In one example, isolation protocols are performedwith isolation valves within the integrated deposition system. Forexample, once a substrate is moved into a lithiation station, isolationvalves shut to cut off the substrate from other stations and forexample, flush with argon or evacuate to prepare for the lithiation. Inanother embodiment, the isolation is achieved by manipulating thecontrolled ambient environment, e.g., by creating a flow dynamic in thecontrolled ambient environment via differential pressures in alithiation station of the integrated deposition system such that thelithium deposition is sufficiently isolated from other processes in theintegrated deposition system. In another embodiment, a combination ofthe aforementioned conditions are used. For example valves can partiallyclose (or the lithiation station can be configured so that the substrateentry and/or exit ports are minimized) and one or more flow dynamics areused to further isolate the lithiation process from adjoining processes.Referring again to FIG. 7C, after the dual lithiation process asdescribed in operations 722-727, the (second) TCO layer is deposited(operation 728) as described above.

FIG. 7D depicts another process flow, 720 b, for depositing the stackonto a substrate. The process is analogous to process flow 700 of FIG.7A. Process flow 720 b includes depositing an EC layer (operation 722)depositing an IC layer (operation 724) and depositing a CE layer(operation 726) as described in relation to FIG. 7B. However, processflow 720 b differs from 720 because there is an intervening lithiationoperation 727. In this embodiment of the process of stack deposition,all the required lithium is added by delivering lithium to the CE layerand allowing the lithium to intercalate into the EC layer via diffusionthrough the IC layer during and/or after stack fabrication. Asmentioned, this may not avoid larger volume changes associated withloading all the required lithium for the device on one side of the IClayer, as the dual lithiation process 720 a does, but it has theadvantage of having one less lithium delivery step.

In certain embodiments, lithiation may occur through a particular methodinvolving sustained self-sputtering. Such methods are further describedin P.C.T. Patent Application No. PCT/US14/35358, filed Apr. 24, 2014,and titled “SUSTAINED SELF-SPUTTERING OF LITHIUM FOR LITHIUM PHYSICALVAPOR DEPOSITION,” which is herein incorporated by reference in itsentirety.

Multistep Thermochemical Conditioning

Referring again to FIG. 7A, once the stack is deposited, the device issubjected to a multistep thermo-chemical conditioning (MTC) process (seeblock 730). Typically, the MTC process is performed only after alllayers of the electrochromic stack have been formed. Some embodiments ofthe MTC process 730 are depicted in more detail in FIG. 7E. Note thatthe MTC process can be conducted entirely ex situ, i.e., outside of theintegrated deposition system used to deposit the stack, or at leastpartially in situ, i.e., inside the deposition system without e.g.breaking vacuum or otherwise moving the substrate outside the controlledambient environment used to fabricate the stack. In certain embodiments,the initial portions of the MTC process are performed in situ, and laterportions of the process are performed ex situ. In certain embodiments,portions of the MTC are performed prior to deposition of certain layers,for example, prior to deposition of the second TCO layer.

Referring to FIG. 7E, and in accordance with certain embodiments, thedevice is first thermally treated under non-reactive conditions (e.g.,under an inert gas). See block 732. In a specific embodiment, the deviceis heated at a temperature of between about 200° C. and about 350° C.for between about 5 minutes and about 30 minutes. In certainembodiments, operation 732 is conducted at low pressure or vacuum.Without wishing to be bound by theory, it is believed that inert gasheating moves any excess lithium from the EC layer to the CE layer, thuscharging the CE layer with lithium (as indicated in some cases by the CElayer's transparency increasing during this process). Next, the deviceis subjected to a thermal treatment under reactive conditions. See block734. In some embodiments, this involves annealing the device in anoxidizing atmosphere (e.g., oxygen and inert gas at about 10-50 mTorr).In specific embodiments, the anneal is conducted at higher pressuresthan the non-reactive thermal processing step (732). In a specificembodiment, the device is heated at a temperature of between about 200°C. and about 350° C. for between about 3 minutes and about 20 minutes.While not wishing to be bound to theory, it is believed that theoxidative anneal process improves the conductivity of the NiWO-basedcounter electrode (which may include one or more additives and/orhalogens as described above) by forming a matrix of Li₂WO₄ (which is avery good lithium ion conductor) that encapsulates individual NiWOgrains. NiWO embedded in a highly ionically conductive matrixfacilitates rapid optical transitions.

Optionally, after the oxidative anneal, the device is heated in air (exsitu). In one embodiment, the device is heated at between about 150° C.and about 500° C. for between about 1 minutes and about 60 minutes, inanother embodiment at between about 200° C. and about 400° C. forbetween about 5 minutes and about 30 minutes, process 736. It should beunderstood that the MTC process may include two, three, or more separateand distinct operations. The three operations described here areprovided solely for purposes of exemplifying the process. Further, theprocess conditions presented here are appropriate for architecturalglass, but may have to be scaled for other applications, recognizingthat the time to heat a device is dependent upon the size of the device.After the MTC process is complete, the device is ready for furtherprocessing.

As mentioned above, additional layers may be needed for improved opticalperformance (e.g. anti-reflectives), durability (due to physicalhandling), hermeticity, and the like. Addition of one or more of theselayers is meant to be included in additional embodiments to thosedescribed above.

Fabrication Process for Completion of the Device

Again referring to FIG. 7A, a second laser scribe (block 740) isperformed. Laser scribe 740 is performed across the length of thesubstrate near the outer edge of the stack, on the two sides of thesubstrate perpendicular to the first laser scribe. FIG. 6B shows thelocation of the trenches, 626, formed by laser scribe 740. This scribeis also performed all the way through the first TCO (and diffusionbarrier if present) to the substrate in order to further isolate theisolated portion of the first TCO layer (where the first bus bar will beconnected) and to isolate the stack coating at the edges (e.g. near amask) to minimize short circuits due to deposition roll off of the stacklayers. In one embodiment, the trench is between about 25 μm and 75 μmdeep and between about 100 μm and 300 μm wide. In another embodiment,the trench is between about 35 μm and 55 μm deep and between about 150μm and 250 μm wide. In another embodiment, the trench is about 50 μmdeep and about 150 μm wide.

Next, a third laser scribe, 745, is performed along the perimeter of thestack near the edge of the substrate opposite the first laser scribe andparallel to the first laser scribe. This third laser scribe is only deepenough to isolate the second TCO layer and the EC stack, but not cutthrough the first TCO layer. Referring to FIG. 6A, laser scribe 745forms a trench, 635, which isolates the uniform conformal portions ECstack and second TCO from the outermost edge portions which can sufferfrom roll off (e.g. as depicted in FIG. 6A, the portion of layers 625and 630 near area 650 isolated by cutting trench 635) and thus causeshorts between the first and second TCO layers in region 650 near wherethe second bus bar will be attached. Trench 635 also isolates roll offregions of the second TCO from the second bus bar. Trench 635 is alsodepicted in FIG. 6B. One of ordinary skill in the art would appreciatethat laser scribes 2 and 3, although scribed at different depths, couldbe done in a single process whereby the laser cutting depth is variedduring a continuous path around the three sides of the substrate asdescribed. First at a depth sufficient to cut past the first TCO (andoptionally the diffusion barrier) along a first side perpendicular tothe first laser scribe, then at a depth sufficient only to cut throughto the bottom of the EC stack along the side opposite and parallel tothe first laser scribe, and then again at the first depth along thethird side, perpendicular to the first laser scribe.

Referring again to process 700, in FIG. 7A, after the third laserscribe, the bus bars are attached, process 750. Referring to FIG. 6A,bus bar 1, 640, and bus bar 2, 645, are attached. Bus bar 1 is oftenpressed through the second TCO and EC stack to make contact with thesecond TCO layer, for example via ultrasonic soldering. This connectionmethod necessitates the laser scribe processes used to isolate theregion of the first TCO where bus bar 1 makes contact. Those of ordinaryskill in the art will appreciate that other means of connecting bus bar1 (or replacing a more conventional bus bar) with the second TCO layerare possible, e.g., screen and lithography patterning methods. In oneembodiment, electrical communication is established with the device'stransparent conducting layers via silk screening (or using anotherpatterning method) a conductive ink followed by heat curing or sinteringthe ink. When such methods are used, isolation of a portion of the firstTCO layer is avoided. By using process flow 700, an electrochromicdevice is formed on a glass substrate where the first bus bar is inelectrical communication with second TCO layer 630 and the second busbar is in electrical contact with first TCO layer 615. In this way, thefirst and second TCO layers serve as electrodes for the EC stack.

Referring again to FIG. 7A, after the bus bars are connected, the deviceis integrated into an IGU, process 755. The IGU is formed by placing agasket or seal (e.g. made of PVB (polyvinyl butyral), PIB or othersuitable elastomer) around the perimeter of the substrate. Typically,but not necessarily, a desiccant is included in the IGU frame or spacerbar during assembly to absorb any moisture. In one embodiment, the sealsurrounds the bus bars and electrical leads to the bus bars extendthrough the seal. After the seal is in place, a second sheet of glass isplaced on the seal and the volume produced by the substrate, the secondsheet of glass and the seal is filled with inert gas, typically argon.Once the IGU is complete, process 700 is complete. The completed IGU canbe installed in, for example, a pane, frame or curtain wall andconnected to a source of electricity and a controller to operate theelectrochromic window.

In addition to the process steps described in relation to the methodsabove, an edge deletion step or steps may be added to the process flow.Edge deletion is part of a manufacturing process for integrating theelectrochromic device into, e.g. a window, where the roll off (asdescribed in relation to FIG. 6A) is removed prior to integration of thedevice into the window. Where unmasked glass is used, removal of thecoating that would otherwise extend to underneath the IGU frame(undesirable for long term reliability) is removed prior to integrationinto the IGU. This edge deletion process is meant to be included in themethods above as an alternative embodiment to those listed above.

Integrated Deposition System

As explained above, an integrated deposition system may be employed tofabricate electrochromic devices on, for example, architectural glass.As described above, the electrochromic devices are used to make IGUswhich in turn are used to make electrochromic windows. The term“integrated deposition system” means an apparatus for fabricatingelectrochromic devices on optically transparent and translucentsubstrates. The apparatus has multiple stations, each devoted to aparticular unit operation such as depositing a particular component (orportion of a component) of an electrochromic device, as well ascleaning, etching, and temperature control of such device or portionthereof. The multiple stations are fully integrated such that asubstrate on which an electrochromic device is being fabricated can passfrom one station to the next without being exposed to an externalenvironment. Integrated deposition systems may operate with a controlledambient environment inside the system where the process stations arelocated. A fully integrated system allows for better control ofinterfacial quality between the layers deposited. Interfacial qualityrefers to, among other factors, the quality of the adhesion betweenlayers and the lack of contaminants in the interfacial region. The term“controlled ambient environment” means a sealed environment separatefrom an external environment such as an open atmospheric environment ora clean room. In a controlled ambient environment at least one ofpressure and gas composition is controlled independently of theconditions in the external environment. Generally, though notnecessarily, a controlled ambient environment has a pressure belowatmospheric pressure; e.g., at least a partial vacuum. The conditions ina controlled ambient environment may remain constant during a processingoperation or may vary over time. For example, a layer of anelectrochromic device may be deposited under vacuum in a controlledambient environment and at the conclusion of the deposition operation,the environment may be backfilled with purge or reagent gas and thepressure increased to, e.g., atmospheric pressure for processing atanother station, and then a vacuum reestablished for the next operationand so forth.

In one embodiment, the system includes a plurality of depositionstations aligned in series and interconnected and operable to pass asubstrate from one station to the next without exposing the substrate toan external environment. The plurality of deposition stations comprise(i) a first deposition station containing a target for depositing anelectrochromic layer; (ii) a second deposition station containing atarget for depositing an ion conducting layer; and (iii) a thirddeposition station containing a target for depositing a counterelectrode layer. The system also includes a controller containingprogram instructions for passing the substrate through the plurality ofstations in a manner that sequentially deposits on the substrate (i) anelectrochromic layer, (ii) an ion conducting layer, and (iii) a counterelectrode layer to form a stack in which the ion conducting layerseparates the electrochromic layer and the counter electrode layer. Inone embodiment, the plurality of deposition stations are operable topass a substrate from one station to the next without breaking vacuum.In another embodiment, the plurality of deposition stations areconfigured to deposit the electrochromic layer, the ion conductinglayer, and the counter electrode layer on an architectural glasssubstrate. In another embodiment, the integrated deposition systemincludes a substrate holder and transport mechanism operable to hold thearchitectural glass substrate in a vertical orientation while in theplurality of deposition stations. In yet another embodiment, theintegrated deposition system includes one or more load locks for passingthe substrate between an external environment and the integrateddeposition system. In another embodiment, the plurality of depositionstations include at least two stations for depositing a layer selectedfrom the group consisting of the electrochromic layer, the ionconducting layer, and the counter electrode layer. Further detailsregarding the deposition system and a mechanism for supporting thesubstrate during deposition are discussed in P.C.T. Patent ApplicationNo. PCT/US14/41569, filed Jun. 9, 2014, and titled “GLASS PALLET FORSPUTTERING SYSTEMS,” which is herein incorporated by reference in itsentirety.

In some embodiments, the integrated deposition system includes one ormore lithium deposition stations, each including a lithium containingtarget. In one embodiment, the integrated deposition system contains twoor more lithium deposition stations. In one embodiment, the integrateddeposition system has one or more isolation valves for isolatingindividual process stations from each other during operation. In oneembodiment, the one or more lithium deposition stations have isolationvalves. In this document, the term “isolation valves” means devices toisolate depositions or other processes being carried out in one stationfrom processes at other stations in the integrated deposition system. Inone example, isolation valves are physical (solid) isolation valveswithin the integrated deposition system that engage while the lithium isdeposited. Actual physical solid valves may engage to totally orpartially isolate (or shield) the lithium deposition from otherprocesses or stations in the integrated deposition system. In anotherembodiment, the isolation valves may be gas knifes or shields, e.g., apartial pressure of argon or other inert gas is passed over areasbetween the lithium deposition station and other stations to block ionflow to the other stations. In another example, isolation valves may beevacuated regions between the lithium deposition station and otherprocess stations, so that lithium ions or ions from other stationsentering the evacuated region are removed to, e.g., a waste streamrather than contaminating adjoining processes. This is achieved, e.g.,via a flow dynamic in the controlled ambient environment viadifferential pressures in a lithiation station of the integrateddeposition system such that the lithium deposition is sufficientlyisolated from other processes in the integrated deposition system.Again, isolation valves are not limited to lithium deposition stations.

FIG. 8A, depicts in schematic fashion an integrated deposition system800 in accordance with certain embodiments. In this example, system 800includes an entry load lock, 802, for introducing the substrate to thesystem, and an exit load lock, 804, for removal of the substrate fromthe system. The load locks allow substrates to be introduced and removedfrom the system without disturbing the controlled ambient environment ofthe system. Integrated deposition system 800 has a module, 806, with aplurality of deposition stations; an EC layer deposition station, an IClayer deposition station and a CE layer deposition station. In thebroadest sense, integrated deposition systems need not have load locks,e.g. module 806 could alone serve as the integrated deposition system.For example, the substrate may be loaded into module 806, the controlledambient environment established and then the substrate processed throughvarious stations within the system. Individual stations within anintegrated deposition systems can contain heaters, coolers, varioussputter targets and means to move them, RF and/or DC power sources andpower delivery mechanisms, etching tools e.g. plasma etch, gas sources,vacuum sources, glow discharge sources, process parameter monitors andsensors, robotics, power supplies, and the like.

FIG. 8B depicts a segment (or simplified version) of integrateddeposition system 800 in a perspective view and with more detailincluding a cutaway view of the interior. In this example, system 800 ismodular, where entry load lock 802 and exit load lock 804 are connectedto deposition module 806. There is an entry port, 810, for loading, forexample, architectural glass substrate 825 (load lock 804 has acorresponding exit port). Substrate 825 is supported by a pallet, 820,which travels along a track, 815. In this example, pallet 820 issupported by track 815 via hanging but pallet 820 could also besupported atop a track located near the bottom of apparatus 800 or atrack, e.g. mid-way between top and bottom of apparatus 800. Pallet 820can translate (as indicated by the double headed arrow) forward and/orbackward through system 800. For example during lithium deposition, thesubstrate may be moved forward and backward in front of a lithiumtarget, 830, making multiple passes in order to achieve a desiredlithiation. Pallet 820 and substrate 825 are in a substantially verticalorientation. A substantially vertical orientation is not limiting, butit may help to prevent defects because particulate matter that may begenerated, e.g., from agglomeration of atoms from sputtering, will tendto succumb to gravity and therefore not deposit on substrate 825. Also,because architectural glass substrates tend to be large, a verticalorientation of the substrate as it traverses the stations of theintegrated deposition system enables coating of thinner glass substratessince there is less concern over sag that occurs with thicker hot glass.

Target 830, in this case a cylindrical target, is oriented substantiallyparallel to and in front of the substrate surface where deposition is totake place (for convenience, other sputter means are not depicted here).Substrate 825 can translate past target 830 during deposition and/ortarget 830 can move in front of substrate 825. The movement path oftarget 830 is not limited to translation along the path of substrate825. Target 830 may rotate along an axis through its length, translatealong the path of the substrate (forward and/or backward), translatealong a path perpendicular to the path of the substrate, move in acircular path in a plane parallel to substrate 825, etc. Target 830 neednot be cylindrical, it can be planar or any shape necessary fordeposition of the desired layer with the desired properties. Also, theremay be more than one target in each deposition station and/or targetsmay move from station to station depending on the desired process.

Integrated deposition system 800 also has various vacuum pumps, gasinlets, pressure sensors and the like that establish and maintain acontrolled ambient environment within the system. These components arenot shown, but rather would be appreciated by one of ordinary skill inthe art. System 800 is controlled, e.g., via a computer system or othercontroller, represented in FIG. 8B by an LCD and keyboard, 835. One ofordinary skill in the art would appreciate that certain embodiments mayemploy various processes involving data stored in or transferred throughone or more computer systems. Certain embodiments also relate to theapparatus, such computers and microcontrollers, for performing theseoperations. These apparatus and processes may be employed to depositelectrochromic materials of methods described herein and apparatusdesigned to implement them. The control apparatus may be speciallyconstructed for the required purposes, or it may be a general-purposecomputer selectively activated or reconfigured by a computer programand/or data structure stored in the computer. The processes presentedherein are not inherently related to any particular computer or otherapparatus. In particular, various general-purpose machines may be usedwith programs written in accordance with the teachings herein, or it maybe more convenient to construct a more specialized apparatus to performand/or control the required method and processes.

As mentioned, the various stations of an integrated deposition systemmay be modular, but once connected, form a continuous system where acontrolled ambient environment is established and maintained in order toprocess substrates at the various stations within the system. FIG. 8Cdepicts integrated deposition system 800 a, which is like system 800,but in this example each of the stations is modular, specifically, an EClayer station 806 a, an IC layer station 806 b and a CE layer station806 c. Modular form is not necessary, but it is convenient, becausedepending on the need, an integrated deposition system can be assembledaccording to custom needs and emerging process advancements. Forexample, FIG. 8D depicts an integrated deposition system, 800 b, withtwo lithium deposition stations, 807 a and 807 b. System 800 b is, e.g.,equipped to carry out methods as described above, such as the duallithiation method described in conjunction with FIG. 7C. System 800 bcould also be used to carry out a single lithiation method, e.g. thatdescribed in conjunction with FIG. 7D, for example by only utilizinglithium station 807 b during processing of the substrate. But withmodular format, e.g. if single lithiation is the desired process, thenone of the lithiation stations is redundant and system 800 c, asdepicted in FIG. 8E can be used. System 800 c has only one lithiumdeposition station, 807.

Systems 800 b and 800 c also have a TCO layer station, 808, fordepositing the TCO layer on the EC stack. Depending on the processdemands, additional stations can be added to the integrated depositionsystem, e.g., stations for cleaning processes, laser scribes, cappinglayers, MTC, etc.

Although the foregoing embodiments have been described in some detail tofacilitate understanding, the described embodiments are to be consideredillustrative and not limiting. It will be apparent to one of ordinaryskill in the art that certain changes and modifications can be practicedwithin the scope of the appended claims.

1-28. (canceled)
 29. An integrated deposition system for fabricating anelectrochromic device stack, the integrated deposition systemcomprising: a plurality of deposition stations aligned in series andinterconnected and operable to pass a substrate from one station to thenext without exposing the substrate to an external environment, whereinthe plurality of deposition stations comprises (i) a first depositionstation containing a first one or more material sources for depositing acathodically coloring layer; (ii) a second deposition station containinga second one or more material sources for depositing an anodicallycoloring layer, wherein the second one or more material sources fordepositing the anodically coloring layer comprise at least a first metaland a halogen, the second one or more material sources for depositingthe anodically coloring layer optionally comprising one ormore-additives, wherein the first metal is selected from the groupconsisting of—chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co),nickel (Ni), rhodium (Rh), and iridium (Ir), ruthenium (Ru), vanadium(V), and combinations thereof, and wherein the optional one or moreadditives are selected from the group consisting of silver (Ag), arsenic(As), gold (Au), boron (B), cadmium (Cd), cesium (Cs), copper (Cu),europium (Eu), gallium (Ga), gadolinium (Gd), germanium (Ge), mercury(Hg), osmium (Os), lead (Pb), palladium (Pd), promethium (Pm), polonium(Po), platinum (Pt), radium (Ra), rubidium (Rb), terbium (Tb),technetium (Tc), thorium (Th), thallium (Tl), tungsten (W), andcombinations thereof; and a controller containing program instructionsfor passing the substrate through the plurality of deposition stationsin a manner that deposits on the substrate (i) the cathodically coloringlayer, and (ii) the anodically coloring layer to form a stack comprisingat least the cathodically coloring layer and the anodically coloringlayer.
 30. The integrated deposition system of claim 29, wherein thesecond one or more material sources for depositing the anodicallycoloring layer together comprise nickel, tungsten, and the halogen. 31.The integrated deposition system of claim 29, wherein the first metal isselected from the group consisting of Cr, Mn, Fe, Co, Ni, Rh, Ir, andcombinations thereof.
 32. The integrated deposition system of claim 31,wherein the first metal is selected from the group consisting of Cr, Mn,Ni, Rh, Ir, and combinations thereof.
 33. The integrated depositionsystem of claim 32, wherein the first metal is selected from the groupconsisting of Ni, Ir, and combinations thereof.
 34. The integrateddeposition system of claim 33, wherein the first metal comprises Ni. 35.The integrated deposition system of claim 29, wherein the second one ormore material sources for depositing the anodically coloring layercomprise the one or more additives, wherein one of the one or moreadditives comprises a material selected from the group consisting of Ga,Gd, Ge, Cu, and combinations thereof.
 36. The integrated depositionsystem of claim 35, wherein one of the one or more additives comprises amaterial selected from the group consisting of Ga, Gd, Ge, andcombinations thereof.
 37. The integrated deposition system of claim 36,wherein one of the one or more additives comprises Ge.
 38. Theintegrated deposition system of claim 36, wherein one of the one or moreadditives comprises Ga.
 39. The integrated deposition system of claim36, wherein one of the one or more additives comprises Gd.
 40. Theintegrated deposition system of claim 35, wherein one of the one or moreadditives comprises Cu.